close

Вход

Забыли?

вход по аккаунту

?

chem.201704978

код для вставкиСкачать
A Journal of
Accepted Article
Title: Heterobimetallic Complexes Featuring Fe(CO)5 as a Ligand on
Gold
Authors: Rasika Dias, Guocang Wang, Tharun T. Ponduru, Qing
Wang, Lili Zhao, and Gernot Frenking
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201704978
Link to VoR: http://dx.doi.org/10.1002/chem.201704978
Supported by
10.1002/chem.201704978
Chemistry - A European Journal
Heterobimetallic Complexes Featuring Fe(CO)5 as a Ligand on Gold
Guocang Wang,† Tharun T. Ponduru,† Qing Wang,‡ Lili Zhao,*,‡ Gernot
†
Department of Chemistry and Biochemistry, The University of Texas at Arlington,
Arlington, Texas 76019, USA;
‡
Institute of Advanced Synthesis, Nanjing Tech
University, Nanjing, 211816, China;
§
Fachbereich Chemie, Philipps-Universität
Marburg, Hans-Meerwein-Strasse, D-35043 Marburg, Germany.
AUTHOR INFORMATION
Corresponding Author
*E-mail: dias@uta.edu
Web: https://www.uta.edu/chemistry/faculty/directory/Dias.php
*E-mail: ias_llzhao@njtech.edu.cn
*E-mail: frenking@chemie.uni-marburg.de
1
This article is protected by copyright. All rights reserved.
Accepted Manuscript
Frenking,*,‡,§ H. V. Rasika Dias*,†
10.1002/chem.201704978
Chemistry - A European Journal
Abstract
Iron(0) pentacarbonyl complexes of gold(I), [Mes3PAu-Fe(CO)5][SbF6] (1) and
[(IPr*)Au-Fe(CO)5][SbF6] (2) (Mes = 2,4,6-trimethylphenyl; IPr* = 1,3-bis(2,6bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) have been synthesized using
Mes3PAuCl and (IPr*)AuCl as the gold(I) precursor, AgSbF6 halide ion abstractor,
pair complexes are significantly shorter than the sum of the experimentally derived
covalent radii of Au and Fe. The (CO) bands of the molecules show a notable blue
shift relative to those observed for free Fe(CO)5, indicating a substantial reduction in
Fe→CO backbonding upon its coordination to gold(I) with either Mes3P or IPr*
supporting ligands (L). The analysis of the electronic structure with quantum
chemical method suggests that the Au-Fe bond consists mainly of [LAu]+←Fe(CO)5 σ
donation and weaker [LAu]+→Fe(CO)5 π backdonation. The donor strength of
Fe(CO)5 is similar to that of CO.
Iron pentacarbonyl is a molecule with a long history.[1] It is an excellent precursor to
access various other iron complexes via carbonyl displacement chemistry with Lewis
bases (L’) such as phosphines, isocyanides, and alkenes leading to molecules of the
type Fe(CO)x(L’)5-x.[2-5] It can also be reduced quite easily to obtain well known
carbonyl ferrates like [Fe(CO)4]2- and [Fe2(CO)8]2-.[6] In these compounds, the iron
center primarily serves as a Lewis acid or an electron acceptor. In contrast, a feature
clearly under-appreciated and relatively less explored concerns donor properties or
Lewis basicity of Fe(CO)5[7] and also of other zero valent metal complexes.[8-13] For
example, structurally authenticated molecules in which Fe(CO)5 acting as a ligand are
2
This article is protected by copyright. All rights reserved.
Accepted Manuscript
and the Lewis base Fe(CO)5. The Au-Fe bond distances of these metal-only Lewis
10.1002/chem.201704978
Chemistry - A European Journal
rare and have appeared in the literature only very recently. They are limited to silver(I)
[B{3,5-(CF3)2C6H3}4]AgFe(CO)5,[14]
complexes
[(Me2Bipy)AgFe(CO)5][B{3,5-
(CF3)2C6H3}4],[14] [(µ-H2O)AgFe(CO)5]2[SbF6]2,[14] [{Fe(CO)5}2(µ-Ag)]Y (Y =
[B{3,5-(CF3)2C6H3}4], [Al{OC(CF3)3}4])[14, 15] and a gallium adduct (CO)5FeGaCl3.[13]
This is surprising considering the ability of metal complexes to act as ligands
albeit involving nickel, and structural data on a “metallo” Lewis acid-base adduct (η5C5H5)(OC)2Co-HgCl2 was reported by Nowell and Russell in 1967.[17] Furthermore,
metal basicity is an important attribute relevant to catalysis, in particular during the
oxidative addition of an element-element bond to a metal site, and for the adduct
formation with certain small molecules, as noted by several groups.[18-22]
P
Au
CO
OC
(1)−AgSbF6
AgCl
Cl
P
CO SbF6
Fe
Au
(2) Fe(CO)5
OC
CO
1
Ph Ph
Ph Ph
N
Ph
Ph
Au
N
Ph
Ph
(1)−AgSbF6
AgCl
N
Ph
OC
Ph
Au
Cl
(2) Fe(CO)5
N
CO
Fe
Ph
Ph OC
Ph
Ph
Ph
Ph
CO
SbF6
CO
2
Scheme 1. Gold(I) complexes of Fe(CO)5, [Mes3PAu-Fe(CO)5][SbF6] (1) and
[(IPr*)Au-Fe(CO)5][SbF6] (2)
3
This article is protected by copyright. All rights reserved.
Accepted Manuscript
resulting in “dative bonds” was recognized in 1964 by Coffey, Lewis, and Nyholm,[16]
10.1002/chem.201704978
Chemistry - A European Journal
An area of focus in our laboratories concerns the chemistry and bonding of
gold(I) adducts involving small molecules such as CO, ethylene, and alkynes.[23-28]
For example, we have reported the isolation of rare Au(I)-CO adducts using
phosphine and N-heterocyclic carbene (NHC) ligand supports.[25, 26, 28] Considering
that the proton affinity of Fe(CO)5 (204 kcal/mol)[29] is higher than that of CO (137.6
analogous Au(I) adducts could be isolated with Fe(CO)5 as a ligand. Although the
large difference in first ionization potentials of Au (9.22 eV)[31] and Fe(CO)5 (7.96
eV)[32] presented a risk of adverse redox processes generating metallic gold from
Au(I), results presented here show that it is indeed possible to synthesize molecules
such as [Mes3PAu-Fe(CO)5][SbF6] (1) and [(IPr*)Au-Fe(CO)5][SbF6] (2) (Scheme 1).
Molecular structures well as a thorough analysis of bonding of these unprecedented
Au-Fe(CO)5 adducts are presented. Such heterometallic complexes are of significant
interest in the study of M-M’ bonding[8, 33-38] and for catalytic applications.[39-43]
Figure 1. Molecular structure of [Mes3PAu-Fe(CO)5][SbF6] (1).
4
This article is protected by copyright. All rights reserved.
Accepted Manuscript
kcal/mol)[30] and the successes with Au(I) complexes of CO, we wanted to see if
10.1002/chem.201704978
Chemistry - A European Journal
Table 1. Selected experimental and calculated (RI-BP86-D3(BJ)/def2-SVP) bond
distances (Å) and angles (°) and CO stretching frequency in IR (cm-1); X = P or C; Ct
and Cc = carbonyl carbon atoms trans- and cis- to Au, respectively
[Mes3PAu-Fe(CO)5][SbF6]
(1)
Exper.
Calc.
Au-Fe
Au-X
X-Au-Fe
Ct-Fe-Au
Fe-Ct
Fe-Cc
2.5671(8)
2.3217(12)
178.16(4)
175.62(17)
1.854(5)
1.840(6)
1.834(7)
1.838(6)
1.828(7)
2.619
2.358
170.8
176.7
1.800
1.834
1.836
1.810
1.807
Au•••Cc
(closest)
Au-Fe-Cc
(smallest)
2.832
CO
[(IPr*)Au-Fe(CO)5][SbF6]
(2)
Exper.
Calc.
2.612
2.032
172.0
168.0
1.792
1.796
1.814
1.837
1.843
2.776
2.5612(7)
2.036(5)
174.56(10)
175.99(15)
1.840(6)
1.834 (5)
1.844(5)
1.844(5)
1.832(5)
2.642
78.3(2)
75.2
71.73(15)
60.0
2140
2088
2052
2151
2105
2078
2060
2041
2143
2095
2073
2057
2147
2106
2076
2058
1959
[Mes3PAu-Fe(CO)5][SbF6]
(1)
has
been
2.320
synthesized
by
treating
[Mes3PAu][SbF6] (generated in-situ from a reaction of Mes3PAuCl[44] and AgSbF6)
with Fe(CO)5 in CH2Cl2 at -20 °C. It is a colorless crystalline solid and characterized
by FT-IR, multinuclear NMR spectroscopy and X-ray crystallography. The solid
samples of 1 are stable in air for several hours at the room temperature. The IR
spectrum of 1 showed several bands (2140, 2088, 2052 cm-1) in the typical terminal
metal carbonyl region that can be assigned to CO vibrational frequencies (Table 1).
All these
CO
bands show a notable blue shift (appear at higher frequencies) relative
to those observed for free Fe(CO)5 (
CO
= 2022, 2000 cm-1 in n-hexane; or 2002, 1979,
1989 cm-1 for pure liquid),[45] indicating significant reduction in the Fe→CO
backbonding due to gold(I) coordination relative to those expected in free Fe(CO)5.
However, these blue shifts are not as high as those observed for the non-classical[46]
5
This article is protected by copyright. All rights reserved.
Accepted Manuscript
Parameter
10.1002/chem.201704978
Chemistry - A European Journal
carbonyl cation [Fe(CO)6]2+ (average 2216 cm-1)[47] that has essentially “σ-only” FeCO bonding.[47]
The molecular structure of 1 depicted in Figure 1, reveals the presence of
[Mes3PAu-Fe(CO)5]+ and [SbF6]− ion-pairs and linearly coordinated gold with a P-AuFe angle of 178.16(4)° (Table 1). There are no close intermolecular Au•••Au
with cis-CO groups slightly bent toward gold (with Au-Fe-cisCO angles ranging from
78.3(2)° to 83.9(2)°, with the closest Au•••cisCO distance of 2.832 Å). According to
calculations of their asymmetry parameter (α),[48] two of the four cis-carbonyls may
be viewed as at the boarder of terminal and semi-bridging (see ESI section for αparameters) while the other two are terminal CO groups.
We have also synthesized a second Au-Fe(CO)5 bonded complex using a NHC
supporting ligand. [(IPr*)Au-Fe(CO)5][SbF6] (2) has been isolated in 68% yield from
a reaction between (IPr*)AuCl[49] and AgSbF6 followed by the treatment with
Fe(CO)5. It also has blue shifted (CO) bands (Table 1) relative to those of the free
Fe(CO)5. X-ray crystal structure of 2 (Figure 2) shows that it has discrete [(IPr*)AuFe(CO)5]+ cations with no intermolecular Au•••Au interactions. The gold and iron
atoms adopt essentially linear (with C-Au-Fe angle of 174.56(10)°) and distorted
octahedral geometries, respectively. The Au-Fe-cisCO angles range from 71.73(15)° to
88.45(15)°. One of the cis-carbonyls of 2 may be considered as semi-bridging with a
Au•••cisCO distance of 2.642(5) Å (α-parameter = 0.44). This distance, however, is
considerably longer than the Au-CO distance of terminal gold-carbonyl adducts, e.g.,
[(SIPr)Au-CO][SbF6] (1.971(5) Å).[25]
6
This article is protected by copyright. All rights reserved.
Accepted Manuscript
interactions. The iron center adopts a distorted octahedral coordination environment
Figure 2. Molecular structure of [(IPr*)Au-Fe(CO)5][SbF6] (2).
The Au-Fe bond lengths of 1 and 2 (2.5671(8) and 2.5612(7) Å, respectively,
Table 1) are similar to the sum of the experimentally derived covalent radii of Au and
Fe (2.68 Å).[50] Although there are no adducts with Au-Fe(CO)5 moiety in the
literature for comparisons with 1 and 2, heterobimetallic gold-iron complexes such as
Ph3PAu-Fe(η3-allyl)(CO)3,[51] Ph3PAu-Fe(SiPh2Me)(CO)3(PPh3)[52] and (IPr)AuFe(η5-Cp)(CO)2[53] based on more nucleophilic and formally anionic iron fragments
are known (in fact, the first Au-Fe complex (Ph3PAu)2Fe(CO)4 was a trinuclear
species synthesized from Ph3PAuCl and [Fe(CO)4]2-)[16,
36]
and they have Au-Fe
bonds with distances at 2.519(1), 2.551(1), and 2.5059(7) Å, respectively. As noted
above, the Fe-CO groups cis-to gold in 1 and 2 show slight bending toward the gold
atom (i.e., the Fe(CO)5 fragment adopts square pyramidal geometry). This type of
slight bending has been observed in the [Ag-Fe(CO)5]+ adducts[14,
15]
and Cl3Ga-
Fe(CO)5 in the literature,[13] and also noted in the computed structure of
[HFe(CO)5]+.[14]
7
This article is protected by copyright. All rights reserved.
Accepted Manuscript
10.1002/chem.201704978
Chemistry - A European Journal
10.1002/chem.201704978
Chemistry - A European Journal
We carried out quantum chemical calculations of the molecules using density
functional theory (DFT) at the RI[54]-BP86[55, 56]-D3(BJ)[57, 58] level using def2-SVP[59]
basis sets for the geometry optimization and def-2TZVPP[60, 61] functions for singlepoint energy calculations. The data in Table 1 show that the calculated geometries of
1 and 2 are generally in good agreement with the experimental values. Note that the
the theoretical Fe-CO(trans) bonds are too short. This suggests that the calculations
probably under- and over-estimate the relative bond strengths of the Au-Fe and FeCO bonds, respectively.
The tilting of two CO groups is also found in the DFT
calculations, where the smallest angle Au-Fe-C is only 60.0o. The analysis of the
electronic structure did not reveal strongly supporting bonding between the CO ligand
and Au (see below). The calculations give also a blue shift for the biggest wave
number relative to Fe(CO)5, which has a calculated value of 2126 cm-1. The optimized
structures and the complete set of bond lengths and angles are given in Supporting
Information along with further details of the method. We also calculated the bond
dissociation energies (BDEs) De of the [LAu-Fe(CO)5]+ (L = NHC or phosphine)
bonds in the cations of 1 and 2 in order to estimate the strength of the gold-iron
bonds. Table 2 shows the results.
Table 2. Bond dissociation energies (in kcal/mol) for ligands dissociation reactions at
the RI-BP86-D3(BJ)/def2-TZVPP// RI-BP86-D3(BJ)/def2-SVP level of theory.
Reactions
[LAu-Fe(CO)5] → [LAu] + Fe(CO)5
[LAu-CO]+
→ [LAu]+ + CO
+
[LAu-Fe(CO)5] → [LAu-Fe(CO)4]+ + CO
Fe(CO)5
→ Fe(CO)4 + CO
+
+
De
L = IPr*
31.9
38.6
47.8
L = IH
45.6
48.8
46.7
L = Mes3P
34.9
34.7
50.4
8
This article is protected by copyright. All rights reserved.
L = Ph3P
37.1
35.7
Accepted Manuscript
calculated Au-Fe bond distances are a bit larger than the experimental values while
10.1002/chem.201704978
Chemistry - A European Journal
The calculations predict that the Au-Fe bond in [(IPr*)Au-Fe(CO)5]+ is a bit
weaker (De = 31.9 kcal/mol) than in [Mes3PAu-Fe(CO)5]+ (De = 34.9 kcal/mol). The
less bulkier parent systems [(IH)Au-Fe(CO)5]+ (IH = NHC with H atoms on the
nitrogens) and [Ph3PAu-Fe(CO)5]+ possess much higher Au-Fe BDEs of De = 45.6
kcal/mol and De = 37.1 kcal/mol, respectively, suggesting a steric effect on the Au-Fe
bulkier IPr* ligand and smaller IH. It seems that the intrinsic electronic effects of the
NHC group leads to stronger Au-Fe bonds compared to those with phosphines on
Au(I) in [LAu-Fe(CO)5]+ systems (L = NHC or phosphine).
Table 3. NBO partial charges q and Wiberg bond index P of the calculated species at
the BP86/def2-TZVPP//RI-BP86/def2-SVP level.
q(Au) q(Fe) q(Fe(CO)5) P(Au-E)a P(Au-Fe)
[Mes3PAuFe(CO)5][SbF6] (1)
0.35 -0.73
0.23
0.52
0.12
[Mes3PAu-Fe(CO)5]+(1-cation frozen)
0.29 -0.73
0.28
0.55
0.12
+
[Ph3PAu-Fe(CO)5]
0.22 -0.74
0.29
0.62
0.12
[(IPr*)Au-Fe(CO)5][SbF6] (2)
0.48 -0.69
0.14
0.58
0.12
+
[(IPr*)Au-Fe(CO)5] (2-cation frozen) 0.46
-0.68
0.18
0.59
0.12
+
[(IH)Au-Fe(CO)5]
0.32 -0.74
0.29
0.63
0.14
Molecule
aE
= C for NHC and L = P for PR3
The Fe(CO)5 fragment in [LAu-Fe(CO)5]+ can be considered as a donor ligand
for the gold cations [LAu]+ (see the bonding analysis below). We also calculated the
cations [LAu-CO]+ in order to compare the donor strength of Fe(CO)5 with CO. The
calculated values in Table 2 suggest that the Fe(CO)5 ligand in [Mes3PAu-Fe(CO)5]+
(De = 34.9 kcal/mol) and [Ph3PAu-Fe(CO)5]+ (De = 37.1 kcal/mol) has a similar donor
strength as CO in the respective phosphine complexes [Mes3PAu-CO]+ (De = 34.7
kcal/mol) and [Ph3PAu-CO]+ (De = 35.7 kcal/mol). The carbonyl ligand in the NHC
9
This article is protected by copyright. All rights reserved.
Accepted Manuscript
bond strength. The difference is most significant between the NHC system with a
10.1002/chem.201704978
Chemistry - A European Journal
complexes [(IPr*)Au-CO]+ (De = 38.6 kcal/mol) and [(IH)Au-CO]+ (De = 48.8
kcal/mol) is only slightly more strongly bonded than Fe(CO)5 in the corresponding
adducts [(IPr*)Au-Fe(CO)5]+ (De = 31.9 kcal/mol) and [(IH)Au-Fe(CO)5]+ (De = 45.6
kcal/mol). As noted above, the Au-Fe bond is probably calculated a bit too weak. The
conclusion is that Fe(CO)5 has a significant donor strength as a ligand in transition
We analyzed the electronic structure of the complexes in order to get insight
on the bonding situation. Table 3 shows the results of the NBO[62] analysis. The
Fe(CO)5 fragment carries a positive charge between +0.14 e and +0.29 e in the NHC
complexes. The positive charge is comparable to the phosphine complexes where
q[Fe(CO)5] is between +0.23 e and +0.29 e. Note that the partial charges in the [LAuFe(CO)5]+ fragments of 1 and 2 are very similar to those of the complete molecules.
The iron atom carries in all species a negative charge while the gold atom is positively
charged, which suggests some electrostatic attraction. The rather small bond orders of
0.12 – 0.14 for the Au-Fe bonds indicate moderate covalent bonding.
More details about the nature of the Au-Fe bond are available from EDA
(Energy Decomposition Analysis) calculations[63] in combination with the NOCV
(Natural Orbitals for Chemical Valence)[64, 65] charge partitioning method. The EDANOCV method has proven to provide deep insight into donor-acceptor interactions.[66]
Table 4 shows the numerical results for the cationic complexes adducts [(IPr*)AuFe(CO)5]+ and adducts [Mes3PAu-Fe(CO)5]+. The intrinsic interaction energies ΔEint
between the frozen fragments [LAu]+ and Fe(CO)5 suggest that the former complex
has a stronger Au-Fe bond than the latter, which agrees with the BDEs. The
contribution of the electrostatic attraction ΔEelstat is larger (52% - 55%) than the
covalent (orbital) bonding ΔEorb (35% - 36%). The dispersion forces provide the
10
This article is protected by copyright. All rights reserved.
Accepted Manuscript
metal complexes, which comes close to that of CO.
10.1002/chem.201704978
Chemistry - A European Journal
remaining 9% - 13% to the total attraction. The ΔEorb term has in both complexes two
major components ΔEorb1 and ΔEorb2. Figure 3 shows the associated deformation
densities Δρ1 and Δρ2 for [Mes3PAu-Fe(CO)5]+ which illustrate the charge flow that is
connected to the orbital interactions. Very similar results were obtained for [(IPr*)AuFe(CO)5]+ (Supporting Information). The direction of the charge migration is
It
becomes
obvious
that
ΔEorb1
comes
from
the
donation
[Mes3PAu]+←Fe(CO)5 while ΔEorb2 comes from the weaker backdonation
[Mes3PAu]+→Fe(CO)5. Inspection of the fragment orbitals, which are connected to
the charge flow, show that Δρ1 arises from charge flow from the HOMO of Fe(CO)5
into the LUMO of [Mes3PAu]+, while Δρ2 comes from the mixture of various
occupied MOs of
[Mes3PAu]+ and the vacant MOs Fe(CO)5. Thus, the orbital
interactions in [LAu-Fe(CO)5]+ can straightforwardly be explained with the DCD
(Dewar-Chatt-Duncanson)[67, 68] model using the frontier orbitals of the fragments.[69]
Table 4. EDA-NOCV results at the BP86-D3(BJ)/TZ2P+ level of the cations [LAuFe(CO)5]+ using the frozen geometries from 1 and 2 cations. The interacting
fragments are [LAu]+ and Fe(CO)5 in the electronic singlet (S) states. Energy values
are given in kcal/mol.
[(IPr*)Au]+ (S) + Fe(CO)5 (S)
-51.7
130.1
[Mes3PAu]+ (S) + Fe(CO)5 (S)
-41.0
99.6
∆Eelstat[a]
-95.1 (52.3 %)
-76.9 (54.7%)
∆Eorb
Fragments
∆Eint
∆EPauli
[a]
-63.4 (34.9 %)
-50.8 (36.1%)
[a]
-23.4 (12.8%)
-13.0 (9.2%)
∆Eorb1[b]
-33.0 (52.1 %)
-32.4 (63.8 %)
∆Eorb2
[b]
-19.7 (31.1 %)
-11.3 (22.2 %)
∆Eorb3
[b]
-4.1 (6.5 %)
-3.4 (6.7 %)
-6.6 (10.4 %)
-3.7 (7.3 %)
∆Edisp
∆Eorb(rest)
aThe
values in parentheses give the percentage contribution to the total attractive interactions
ΔEelstat + ΔEorb + ∆Edisp.
bThe values in parentheses give the percentage contribution to the total orbital interactions ΔE .
orb
11
This article is protected by copyright. All rights reserved.
Accepted Manuscript
red→blue.
10.1002/chem.201704978
Chemistry - A European Journal
ΔEorb(2) = -11.3 kcal/mol
Figure 3. Plot of deformation densities Δρ1-3 of the pairwise orbital interactions
between the two fragments in their singlet (S) states in the frozen [Mes3PAuFe(CO)5]+ fragment of 1 together with the associated interaction energies ΔEorb (in
kcal/mol). The direction of charge flow is red→blue.
In summary, we report the first examples of Au-Fe(CO)5 adducts. Molecules
like [Mes3PAu-Fe(CO)5][SbF6] and [(IPr*)Au-Fe(CO)5][SbF6] are of interest since
they represent metal only Lewis pairs with a direct link between two catalytically very
important metal ions (Au and Fe),[70-75] and may show new reactivity through
harnessing the cooperativity between disparate metal sites.[8, 40, 43] The analysis of the
electronic
structure
suggests
that
the
Au-Fe
bond
comes
mainly
from
[LAu]+←Fe(CO)5 σ donation and weaker [LAu]+→Fe(CO)5 π backdonation. The
donor strength of Fe(CO)5 is similar to that of CO.
Acknowledgments. This work was supported by the Robert A. Welch Foundation
(Grant Y-1289). L. Zhao and G. Frenking gratefully acknowledge financial
support
from
grant
numbers
39837132,
39837123,
BK20170964,
and
NSF:21703099 of China and a SICAM Fellowship from Jiangsu National
Synergetic Innovation Center for Advanced Materials.
12
This article is protected by copyright. All rights reserved.
Accepted Manuscript
ΔEorb(1) = -32.4 kcal/mol
10.1002/chem.201704978
Chemistry - A European Journal
Experimental Section.
Experimental details are provided in the supporting information section
Supporting Information Available: X-ray crystallographic data (CIF) for CCDC
1577914-1577915, tables of selected bond distances and angles, additional figures
molecules are also given.
References:
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
L. Mond, C. Langer, J. Chem. Soc. Trans. 1891, 59, 1090-1093.
M. O. Albers, E. Singleton, N. J. Coville, A. Y. J. Chen, R. Blanski, H. D.
Kaesz, in Inorg. Synth., Vol. 28, John Wiley & Sons, Inc., Hoboken, NJ, USA.,
1990, pp. 179-186.
M. J. Therien, W. C. Trogler, R. Silva, M. Y. Darensbourg, in Inorg. Synth., Vol.
28, John Wiley & Sons, Inc., Hoboken, NJ, USA, 1990, pp. 173-179.
K. H. Whitmire, A. T. Kelly, C. Hofmann, in Comprehensive Organometallic
Chemistry III (Ed.: R. H. Crabtree), Elsevier, Oxford, 2007, pp. 1-75.
R. C. Kerber, in Comprehensive Organometallic Chemistry II (Eds.: F. G. A.
Stone, G. Wilkinson), Elsevier, Oxford, 1995, pp. 101-229.
H. Strong, P. J. Krusic, J. S. Filippo, S. Keenan, R. G. Finke, in Inorg. Synth.,
Vol. 24, John Wiley & Sons, Inc., New York, 1986, pp. 157-161.
P. A. W. Dean, D. G. Ibbott, G. M. Bancroft, J. Chem. Soc., Chem. Commun.
1976, 901-902.
J. Bauer, H. Braunschweig, R. D. Dewhurst, Chem. Rev. 2012, 112, 4329-4346.
S. Coco, P. Espinet, F. Mayor, X. Solans, J. Chem. Soc., Dalton Trans. 1991,
2503-2509.
F. Jiang, J. L. Male, K. Biradha, W. K. Leong, R. K. Pomeroy, M. J.
Zaworotko, Organometallics 1998, 17, 5810-5819.
D. V. Khasnis, H. Le Bozec, P. H. Dixneuf, R. D. Adams, Organometallics
1986, 5, 1772-1777.
H. Le Bozec, P. H. Dixneuf, R. D. Adams, Organometallics 1984, 3, 19191921.
H. Braunschweig, R. D. Dewhurst, F. Hupp, C. Kaufmann, A. K. Phukan, C.
Schneider, Q. Ye, Chem. Sci. 2014, 5, 4099-4104.
G. Wang, Y. S. Ceylan, T. R. Cundari, H. V. R. Dias, J. Am. Chem. Soc. 2017,
DOI: 10.1021/jacs.1027b08595.
P. J. Malinowski, I. Krossing, Angew. Chem., Int. Ed. 2014, 53, 13460-13462.
C. E. Coffey, J. Lewis, R. S. Nyholm, J. Chem. Soc. 1964, 1741-1749.
I. N. Nowell, D. R. Russell, Chem. Commun. 1967, 817.
L. Vaska, Acc. Chem. Res. 1968, 1, 335-344.
J. P. Collman, W. R. Roper, Adv. Organomet. Chem. 1969, 7, 53-94.
13
This article is protected by copyright. All rights reserved.
Accepted Manuscript
and details. Optimized structures, calculated coordinates and energies of the reported
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
D. F. Shriver, Acc. Chem. Res. 1970, 3, 231-238.
L. Vaska, Inorg. Chim. Acta 1971, 5, 295-300.
H. Werner, Angew. Chem. Int. Ed. 1983, 22, 927-949.
H. V. R. Dias, J. Wu, Angew. Chem. Int. Ed. 2007, 46, 7814-7816.
H. V. R. Dias, M. Fianchini, T. R. Cundari, C. F. Campana, Angew. Chem. Int.
Ed. 2008, 47, 556-559.
C. Dash, P. Kroll, M. Yousufuddin, H. V. R. Dias, Chem. Commun. 2011, 47,
4478-4480.
H. V. R. Dias, C. Dash, M. Yousufuddin, M. A. Celik, G. Frenking, Inorg.
Chem. 2011, 50, 4253-4255.
A. Das, C. Dash, M. Yousufuddin, M. A. Celik, G. Frenking, H. V. R. Dias,
Angew. Chem. Int. Ed. 2012, 51, 3940-3943.
M. A. Celik, C. Dash, V. A. K. Adiraju, A. Das, M. Yousufuddin, G. Frenking,
H. V. R. Dias, Inorg. Chem. 2013, 52, 729-742.
M. S. Foster, J. L. Beauchamp, J. Am. Chem. Soc. 1975, 97, 4808-4814.
A. N. Hayhurst, S. G. Taylor, Phys. Chem. Chem. Phys. 2001, 3, 4359-4370.
H.-P. Loock, L. M. Beaty, B. Simard, Phys. Rev. A 1999, 59, 873-875.
D. R. Lloyd, E. W. Schlag, Inorg. Chem. 1969, 8, 2544-2555.
L. H. Gade, Angew. Chem. Int. Ed. 2000, 39, 2658-2678.
S. T. Liddle, Molecular Metal-Metal Bonds, Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim, Germany, 2015.
P. Pyykkö, Chem. Rev. 1997, 97, 597-636.
S. Sculfort, P. Braunstein, Chem. Soc. Rev. 2011, 40, 2741-2760.
H. Schmidbaur, A. Schier, Chem. Soc. Rev. 2012, 41, 370-412.
T. G. Gray, J. P. Sadighi, in Molecular Metal-Metal Bonds, Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim, Germany, 2015, pp. 397-428.
J. F. Berry, C. C. Lu, Inorg. Chem. 2017, 56, 7577-7581.
P. Buchwalter, J. Rosé, P. Braunstein, Chem. Rev. 2015, 115, 28-126.
I. G. Powers, C. Uyeda, ACS Catal. 2017, 7, 936-958.
M. K. Karunananda, N. P. Mankad, J. Am. Chem. Soc. 2015, 137, 1459814601.
J. Campos, J. Am. Chem. Soc. 2017, 139, 2944-2947.
R. C. Bott, G. A. Bowmaker, R. W. Buckley, P. C. Healy, M. C. S. Perera, Aust.
J. Chem. 2000, 53, 175-181.
Y. Jiang, T. Lee, C. G. Rose-Petruck, J. Phys. Chem. A 2003, 107, 7524-7538,
and the references therein.
A. J. Lupinetti, S. H. Strauss, G. Frenking, Prog. Inorg. Chem. 2001, 49, 1-112.
E. Bernhardt, C. Bach, B. Bley, R. Wartchow, U. Westphal, I. H. T. Sham, B.
von Ahsen, C. Wang, H. Willner, R. C. Thompson, F. Aubke, Inorg. Chem.
2005, 44, 4189-4205.
M. D. Curtis, K. R. Han, W. M. Butler, Inorg. Chem. 1980, 19, 2096-2101.
A. Gómez-Suárez, R. S. Ramón, O. Songis, A. M. Z. Slawin, C. S. J. Cazin, S.
P. Nolan, Organometallics 2011, 30, 5463-5470.
B. Cordero, V. Gomez, A. E. Platero-Prats, M. Reves, J. Echeverria, E.
Cremades, F. Barragan, S. Alvarez, Dalton Trans. 2008, 2832-2838.
F. E. Simon, J. W. Lauher, Inorg. Chem. 1980, 19, 2338-2343.
U. Schubert, E. Kunz, M. Knorr, J. Müller, Chem. Ber. 1987, 120, 1079-1085.
M. K. Karunananda, S. R. Parmelee, G. W. Waldhart, N. P. Mankad,
Organometallics 2015, 34, 3857-3864.
K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett.
14
This article is protected by copyright. All rights reserved.
Accepted Manuscript
10.1002/chem.201704978
Chemistry - A European Journal
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
1995, 242, 652-660.
A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100.
J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824.
S. Grimme, S. Ehrlich, L. Goerigk, J. Comput. Chem. 2011, 32, 1456-1465.
S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 2010, 132, 154104.
A. Schäfer, h. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577.
F. Weigend, M. Häser, H. Patzelt, R. Ahlrichs, Chem. Phys. Lett. 1998, 294,
143-152.
F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 2005, 7, 3297-3305.
http://nbo6.chem.wisc.edu/
T. Ziegler, A. Rauk, Theor. Chim. Acta 1977, 46, 1-10.
M. Mitoraj, A. Michalak, Organometallics 2007, 26, 6576-6580.
M. Mitoraj, A. Michalak, J. Mol. Model. 2008, 14, 681-687.
M. P. Mitoraj, A. Michalak, T. Ziegler, J. Chem. Theory Comput. 2009, 5, 962975.
J. Chatt, L. A. Duncanson, J. Chem. Soc. 1953, 2939-2947.
M. J. S. Dewar, Bull. Soc. Chim. Fr. 1951, C71-79.
K. Fukui, T. Yonezawa, H. Shingu, J. Chem. Phys. 1952, 20, 722-725.
A. S. K. Hashmi, Chem. Rev. 2007, 107, 3180-3211.
A. Arcadi, Chem. Rev. 2008, 108, 3266-3325.
D. J. Gorin, B. D. Sherry, F. D. Toste, Chem. Rev. 2008, 108, 3351-3378.
Z. Li, C. Brouwer, C. He, Chem. Rev. 2008, 108, 3239-3265.
C. Bolm, J. Legros, J. Le Paih, L. Zani, Chem. Rev. 2004, 104, 6217-6254.
A. Fürstner, ACS Cent. Sci. 2016, 2, 778-789.
15
This article is protected by copyright. All rights reserved.
Accepted Manuscript
10.1002/chem.201704978
Chemistry - A European Journal
10.1002/chem.201704978
Chemistry - A European Journal
TOC Content
Cationic gold center captures an iron pentacarbonyl molecule as a ligand forging a
CO
OC
P
Fe
Au
OC
CO
CO
16
This article is protected by copyright. All rights reserved.
Accepted Manuscript
heterobimetallic gold-iron linkage
Документ
Категория
Без категории
Просмотров
2
Размер файла
1 023 Кб
Теги
201704978, chem
1/--страниц
Пожаловаться на содержимое документа