вход по аккаунту


Coinage Metal Complexes of HexaphenylcarbodiphosphoraneЦOrganometallic Compounds with Coordination Number 2.

код для вставкиСкачать
Coinage Metal Complexes of
Hexaphenylcarbodiphosphorane- Organometallic
Compounds with Coordination Number 2
By Hubert Schmidbaur*, Christian E. Zybill,
Gerhard Miiller, and Carl Kriiger
Dedicated to Professor Ulrich Wannagat on the occasion
of his 60th birthday
In organometallic compounds with gold in the oxidation
state + 1 the coordination number never as a rule exceeds
2, whereas with the lighter "coinage metals" this lower
coordination number is exceptionally rare"]. Among the
few structurally characterized copper compounds with
simple aliphatic ligands we find, besides the (trimethylsilylmethyl)copper(I) tetramerI2I, also the dinuclear ylide
complex la[3a1,in which two linear CH2CuCH2groups are
arranged parallel to each other. The corresponding silver
and gold compounds l b and l c , respectively, have an
analogous structure[3b1.
la: M
lb: M
Ic: M
c .sin 3
= CU
Fig. 1. Projection of a section from the crystal lattice of the copper complex
We now report on the synthesis of coinage metal complexes of the double ylideL4]hexaphenylcarbodiphosphorane 2, in which the strictly linear twofold coordination is
ensured in all cases by the specific (especially steric) effect
of the new ligand, even although the second ligand is a
halide capable of functioning as a donor.
Suspensions of anhydrous CuCl or AgCl in tetrahydrofuran rapidly clarify on addition of a solution of 2 in the
same solvent, and the reaction products 3a and 3b, respectively, crystallize from the mixtures on cooling. For the
preparation of 3c it is more advantageous to use
(C0)AuCl as starting material, with removal of CO.
(122.1(1) and 113.7(1)", respectively); PI-CI-P2
123.8(1)" and is thus smaller than the corresponding angle
in 2. The especially interesting Cl-Cu distance of
1.906(2) A corresponds to a Cu-C(sp2) bond, as also exists, for -example, in the bis(mesityl)copper( 1 -) ion
(1.915(9) A[6a1).
3 a : ILI = C u
3b: M = Ag
3c: M = Au
None of the three products[5a1is sensitive to air, and all
are thermally stable up to ca. 200°C. Solutions of 3a, 3b
and 3c in CD2CI, show 3'P('H]-NMR singlet signals at
6= 16.5, 16.5, and 13.7, respectively. In the "C-NMR
spectra the signal of the ylidic C-atom is not observable;
the phenyl signals conform to expectation [e.g. 3b:
6=132.6, AA'X, Nz95.7 Hz, C-1; 127.9(4.9), C-2; 132.3,
br, C-3 ; 130.8(4.9), C-41.
The X-ray structure analysis of 3a shows[sb1that discrete
molecules are present in the crystal, between which there
are no unusually short contacts (Fig. 1). The ligand arrangement at the copper atom is practically linear with
Cl-Cu-Cl = 178.2(1)", while that at the yljdic carbon
atom (Cl) is trigonal planar. C1 is only 0.056 A outside of
the CuPlP2 plane, whereas the chlorine atom lies, within
the standard deviation, in the plane (Fig. 2). The angles
PI-Cl-Cu and P2-Cl-Cu, however, are very different
[*] Prof. Dr. H. Schmidbaur, Dr. C . E. Zybill
Fig. 2. Molecular structure of 3a
angles are given in the text.
the crystal [5b]. Some bond distances and
The compounds 3 are especially suitable for the synthesis of further lower coordinated organometallic derivatives.
Reaction of anhydrous CuC1, with 2 does not lead to
Cu" coordination compounds but to reduction of the copper and oxidative halogenation of the carbodiphosphorane
to give the salt 4['"l [6(P)=26.8, s; 6(PCP)= 192, t,
zJ('3P'3C)= 113.3 H z ' ~ ~v(CuC1,)=385
Anorganisch-chemisches Institut der Technischen Universitit Miinchen
Lichtenbergstr. 4, D-8046 Garching (Germany)
Prof. Dr. C . Kriiger, Dr. G. Muller
Max-Planck-Institut fur Kohlenforschung
Kaiser-Wilhelm-Platz 1, D-4330 Miilheim a. d. Ruhr (Germany)
Angew. Chem. I n i . Ed. Engl. 22 (1983) No. 9
0 Verlag Chemie GmbH, 6940 Weinheim, 1983
0570-0833/83/0909-0729 $02.S0/0
This behavior of 2 is in complete contrast to that of the
simple ylides, which under comparable conditions undergo oxidative coupling to give bisphosphonium salts16c1.
Received: May 2, 1983 [ Z 372 IE]
German version: Angew. Chem. 95 (1983) 753
[I] Gold, silver: Gmelin Handbuch der Anorganischen Chemie, 8th Edit.,
Springer, Berlin 1975 and 1980; Copper: A. E. lukes, Adu. Organomet.
Chem. 12 (1974) 215; F. H. Jardine, Adu. Inorg. Chem. Radiochem. 17
(1975) 116.
121 M. F. Lappert, R. Pearce, J. Chem. Soc. Chem. Commun. 1973, 24; I. A. J.
Jarvis, B. T. Kilbourn, R. Pearce, M. F. Lappert, ibid. 1973, 475.
131 a) H. Schmidbaur, I. Adlkofer, M. Heimann, Chem. Ber. ?07(1974) 3697;
H. Schmidbaur, J. Adlkofer, W. Buchner, Angew. Chem. 85 (1973) 448;
Angew. Chem. I n t . Ed. Engl. I2 (1973) 415; P. K. Mehrotra, R. Hoffmann, Inorg. Chem. 17 (1978) 2187; G. Nardin, L. Randaccio, E. Zangrando, J. Organomet. Chem. 74 (1974) C23; - b) H. Schmidbaur, W.
Richter, Chem. Ber. 108 (1975) 2656; Y. Yamamoto, H. Schmidbaur, J.
Organomet. Chem. 96 (1975) 133; 97 (1975) 479; H. Schmidbaur, J. R.
Mandl, W. Richter, V. Bejenke, A. Frank, G. Huttner, Chem. Ber. 110
(1977) 2236; J. Stein, I. P. Fackler, C. Paparizos, H. W. Chen, J. Am.
Chem. Soc. 103 (1981) 2192.
141 H. Schmidbaur, Nachr. Chem. Tech. Lab. 27 (1979) 620.
[5] a) Procedure: A solution of 2 (444 mg, 0.83 mmol) in tetrahydrofuran
(THF) (30 mL) is added dropwise to a suspension of anhydrous CuCl(82
mg, 0.83 mmol) in THF (10 mL), whereupon the CuCl almost completely
dissolves. After filtration and cooling to O T , 3a crystallizes as yellow
cubes, m. p. 241 "C (decomp.), yield 486 mg (92Oh).- 3b is obtained in an
analogous way, but as the THF-monoadduct, m.p. 234"C, yield 90%.Colorless crystals of the THF-monoadduct of 3c (decomp. 250"C, yield
87%) are likewise formed on reaction of (C0)AuCI and 2 in THF.-The
preparation of 4 is analogous to that of 3a. The product is very sparingly
soluble in THF and is recrystallized from dichloromethane. Colorless
cubic crystals (CH2C12-monoadduct), m.p. 210-212 (decomp.), yield
63%. b) Crystallographic data: C3,H30CICuP2 (635.5983); P2,/c, 2 = 4 ;
C = 17.935(1) A,
p = 100.663(7)",
v=3151.35 A3, pca,c =1.3396 g c m - ) ; MO,,, a2=o.7i069A, T = ~ I " C ,
scano-28, 1.0<3<28.9", 8289 independent reflections, 2895 unobserved (I<2o(I)), heavy atom method (SHELX-76), H atoms observed at
R = 0.059; from 490 refined parameters R = 0.0395, R , = 0.0464. Further
details of the crystal structure investigation are obtainable on request
from the Fachinformationszentrum Energie Physik Mathematik, D-75 14
Eggenstein-Leopoldshafen, on quoting the depository number CSD
50442, the names of the authors, and full citation of the journal.
[6] a) P. Leoni, M. Pasquali, C. A. Ghilardi, J. Chem. Soc. Chem. Commun.
1983, 240; b) R. Appel, F. Knoll, W. Michel, W. Morbach, H. D. Wihler,
H. Veltmann, Chem. Ber. 109 (1976) 5 8 ; c) G. A. Bowmaker, C. DOEbach, H. Schmidbaur, unpublished.
:Synthesis and Reactions**
By Gerhard Fritz* and Heinz Bauer
Dedicated to Professor Ulrich Wannagat on the occasion
of his 60th birthday
The synthesis and reactive behavior of organosilicon
compounds containing CF, groups have to our knowledge
never been described in the literature. Reports have appeared, however, on NMR investigations of perfluoroalkylsilanesrl"l obtained by reaction of CF31 with SiFZ[lb'.
C-Fluorinated carbasilanes are of interest in view of the
known reactions of C-chlorinated compounds such as
(C13Si)zCCl,'za1 or (C12Si-CClz)3[2bl;e. 9.. lithiation of the
CCI2 group in (C12Si-CC12)3 leads to ring contraction and
ring opening12b1,
and in the case of C1MezSi(Me3Si)CCl2to
ring closure with formation of a 2,4-disilabicyclo[1.1 .O]butanel*''.
Insertion of the carbene CF,, generated by thermolysis
of Me3SnCF313a1,
into the SiSi bond of (FMe2Si)2[3b1
according to
+ :CF2
to formation of the new compound 1, which we were able
to isolate from the reaction mixture by gas chromatograp h ~ ' ~At
' . room temperature, and in the absence of air and
moisture, 1 is a stable, colorless liquid, b.p. 161.6"C (extrapolated from the vapor pressure curve).
Unlike the corresponding C-chlorinated carbasilanes, 1
reacts with MeMgCl or MeLi, even at low temperatures,
not with C-metalation but with Si-alkylation to give the
products 2 and 3[". Reaction of 1 with PhMgBr or PhLi
analogously yields the phenyl derivatives 4 and 5 . That
is, neither a CF- nor a CSi-cleavage takes place. Reaction
of 1 with LiAIH, leads, depending upon the molar ratio, to
6 and 7I4I.In all cases the CF2 group remains inert.
2: R = M e
4 : R=Ph
6 :R=H
3: R = M e
5 : R=Ph
7: R = H
Table 1. Spectroscopic data of the compounds 1-8.
1: MS (EI): m / z Si2CSHI2F4
204.04 deviation-1.1; 'H-NMR: 6=0.32 (m),
higher order; "CI'HJ-NMR: 6=103.0 (t) CHI, -24.0 (d) CF,, 'JCF=260,
'Jc~=25.9 Hz; I9F-NMR: 6=144.7 (m) FC, 166.0 (m) FSi, spin system
X&Y2X'&; '9Si{'H)-NMR: 6=20.35 (m), 'JS,~=290.4,'JSrF=36.O Hz
2: m / z 200.07, deviation 2.0; 6('H)=0.18 (m) Me3Si, 0.28 (dt) Me2Si,
4 J n ~ = o . 8HZ; S("C('HJ)=97.2 (dt) CF2, -25.0 (dt) Me,Si, -25.4
(dt) Mez% ' J c ~ = 2 5 5 , 2 J c ~ = 2 6 ,'Jh1.~=13 Hz;6(l9F)=341 (d) FC, 165
. ~6(29Si('H})=1.43 (t) SiMe,,
(Sept) FSi, ' J F H = ~ . ~ , 4 J ~ ~ = o . '8J, F F = ~
20.43 (dt) SiMe2, 'JscF=285, 2Js,F=37.5 and 27.8 Hz
3 : m / r 196.02, deviation - 1.0; 6('H)=0.10 (t), 4JHF=0.7 Hz; 6(l9F)= 136.4
4: 6('H)=0.43 (dm) Me,SiF, 0.15 (m) Me'SiPh, 7.49 (m)Ph, 'JHF=7.2 Hz;
6("F)= 143.1 (d) FC, 159.0 (3 X 7) FSI, ' J F ~ z 7 . 2 , ' 3 ~ ~ ~ HZ
6 . 4
5:6('H)=0.18 (t) Me, 7.32 (m) Ph, 4JHF=0.6Hz; 6(I9F)=133.5 (m)
6 : 6('H)=0.4 (d) MeSiF, 0.12 (d) Me,SiH, 4.08 (3x7) HSi, 3JHF=4.6,
' J H F = ~ . ~ Hz; 6(I9F)=137.3 (dd) FC, 156.0 (sept) FSi, 3JFF=6.8
7:6('H)=0.2(d) Me2Si,4.03 (m) HSi, 3JHH=3.8,' J H F = l l Hz;6(19F)=135.7
8 : 6('H)=0.41 (d) M e A 1.28 (ddt) Me2PC, 0.92 (ddt) Me,PP, ,JHF=7.2,
11.6 and 5.1, 'JHP=
16.1 and 3.9 Hz; S("P('H})=9.1 (dt) P=C, -59.5
(dm) PP, 'JPp=212.8, 'JPF=2.6 Hz
NMR data measured on 1 and 2 in C6Da/CC14/C6F6, on 3 to 1 in
Et20/C6D6/C6Fbr On 8 in CsH.dCsD6 ['H (80 and 300 MHz); "C (75.46
MHz), 29Si (59.26 MHz), ''P (121.49 MHz); I9F (84.6 MHz)]
It is well known that C-chlorinated carbasilanes cleave the
SIP bond in silylphosphanes with formation of the ylide""].
Thus, (C13Si)2CC12 reacts with Me3Si-PMe2 to give
(C13Si),C=PMe2C1. The CF, group in 1 is also capable of
undergoing this reaction, as is shown by the formation of
the ylide 8.
+ Me+PMe,
0 Verlag Chemie GmbH. 6940 Weinheim. 1983
-M~,SIF{ (FMe2Si)zCF-PMez)
['I Prof. Dr. G. Fritz, H. Bauer
Institut fur Anorganische Chemie der Universitat
Postfach 63 80, D-7500 Karlsruhe 1 (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft
(FMezSi) z C = P M e r P M e z
0570-0833/83/0909-0730 $ 02.50/0
+ M e SrPMe
{(FMezSi) zC=PMefl]
Angew. Chem. Int. Ed. Engl. 22 (1983) No. 9
Без категории
Размер файла
236 Кб
coinage, compounds, metali, coordination, number, hexaphenylcarbodiphosphoraneцorganometallic, complexes
Пожаловаться на содержимое документа