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Novel Carbon Compounds with УNakedФ Cn Units.

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HIGHLIGHTS
Novel Carbon Compounds with “Naked” C, Units
Heinrich Lang*
[L,M=C - M‘L,]
[(tpp)Fe=C = ML,]
1
2
l a : M L , = Re,(CO), [4]
1 b:ML, = Mn,(CO), [3]
lc:ML,, = Cr(CO), 13)
Id:ML, = Fe(CO), [3]
2a:ML, = HB(pz),(CO),Mo; M‘L, = FeCp(CO), [Sa]
2b:ML, = HB(pz),(CO),Mo; M‘L, = PtBr(PPh,), [Sb]
2c:ML, = (Me,CO),W; M’L, = RuCp(CO), [Sc]
A new class of compounds interesting in view of their new
material properties”] and as model systems for surface carbides
in heterogeneous catalysis[’, 31 has become significant: compounds in which linear carbon chains C , (n = 1 - 5 ) bridge different organometallic building blocks. Whereas compounds with
“naked” C,, units (n = 1,2, 4) and identical terminal metal complex fragments have already been well studied,L3]complexes with
C,, bridges ( n = 1-5) which link different transition metal complex building blocks have only recently become accessible.[1 e . 3
~
I81
With regard to the synthesis of complexes with C , bridges a
formal classification of these compounds into those with an
even number of CZn( n = 1,2. . . .) bridges and those with an odd
numbcr of C,,,, ( n = 0, 1. 2, . . . j bridges is possible.
Transition Metal Complexes with C,,
+
this synthetic method to the carbonyl metalates [Mn(CO)J,
[Cr(C0),l2-, and [Fe(CO),]*- leads to the compounds 1 b-d.[31
The complex 2 a can be prepared by nucleophilic substitution
of [{HB(pz),)(CO),Mo-CCI]
(pz = 3,5-dimethylpyrazolyI)
with K[FeCp(COj,];[5”1 2 b is formed by the reaction of the
Units (n = 0, 1, 2)
c‘, Bri&c,s: Organonietallic compounds with a single carbon
atom between two different metal atoms are of interest as model
systems for surface carbides.[“% ’I The two-coordinate carbon
atom may be part of a 1,3-dimetallaallene system as in 1[3.4’o r
part of a C-metalated carbyne complex (2).[51
Whereas the synthesis, the reaction behavior, and the structural features of 1.3-dimetallaallenes of the higher homologues
of carbon have been wellstudied.LL”- 2 2 1 only few examples of isolated and structurally characterized carbon
compounds such as 1 are
known.’”‘’ One of these compounds is the 1.3-dimetallaallene l a synthesized by W.
Beck et al., which contains the
shortest metal-carbon bond
(Fe-C: 161 pin) known so
far.’“ Compound l a was obtained by the reaction of
the dichlorocarbene complex
5a
[(tpp)Fe=CCI,J (tpp = tetraScheme I . 4 a : ML,, = Re(CO),Re(CO),;
phenylporphyrinate)
with
[Re(CO),]-. The extension of
Re
ON’
Anor@ani,ch-chemischer lnstitut der Univers&it
Im Keucnheimer Feld 270. D-69120 Heidelberg (FRC;)
Telef;ix: 1111. code + (6221)56-4197
Re
‘PP~,
O
!N’
‘PPh,
11
~
[*I Prib -Do/. Dr. H Lang
1
C
C
1
4
//“OMe
L“M
4a
I
4b
I
c
oc,
C
Ill @ A 0
V”
6a
5b
4 b : ML,
It
BF,O
= CpMn(CO),; 4 c :
ML, =W(CO),; 4 d : ML,
6b
=
Fe(CO),.
analogous bromocarbyne with “Pt(PPh3)2”.[3,5b1 A particularly
elegant synthetic method makes use of the alkyne-analogous
reactivity of [(Me,CO),W-CEt] which in the metathesis with
the alkyne complex [Cp(CO),Ru-C=CMe] affords the C-metalated carbyne complex ~ c . [ ~ “ I
HIGHLIGHTS
C , und C , Bridges: By using the classic Fischer-carbene and
-carbyne synthesis,"] J. A. Gladysz et al. were able to prepare
complex 5 in a two-step reaction sequence; this compound exhibits a novel nonlinear form of a C, bridge (Scheme
The
synthesis of this compound is achieved by treating the acetylide
complex 3 first with [Re,(CO),,]/Me,OBF, and subsequently
with BF,. If the mononuclear carbonyl complexes [CpMn(CO),],[Fe(CO),], or [W(CO),] are used instead of [Re,(CO),,],
initially compounds 4 b - d are formed by an analogous reaction
pathway; subsequent reaction of 4 b with BF, leads to the
cationic complex 6,1Ta1
which, in contrast to 5, has a linear,
terminally bound C, chain.
The structures of compounds 5 and 6 have been confirmed by
X-ray structure analyses.[71Thus, the structure of compound 6
can best be described by the "curnulene formula" 6b.I" The
Re-C and C-C distances in 5 correspond best to the limiting
structure 5b.[7b1
which is consistent with the stronger donor
properties of the Ph,P- and Cp*-substituted rhenium atom.
The successful strategy for the preparation of complexes 5
and 6 could be extended to the synthesis of compound 9 containing a C, chain.[*]A decision as to which of the two given limiting
formulae is more important for 9 may only be reached by a
structure anaIysis.[']
are bound to the C, unit, such as in [(CO),Re-C-C-Re(C0),].[9'
In general. the synthesis of compounds with two different
metal complex fragments at the C, building block requires first
the preparation of the
organometallic-subCI
stituted alkyne. ComI
pound 10 is formed in
Me3P-Pt-PMe3
I
Me3P'p'PMe,
this way by the reacC
C
Ill
tion of [(Me,P),(CI)r:111r
Pt-C-CHI
with
I
I
9
I
Zr
Me,P - Pd-PMe,
[(Me,P),PdCI,] in the
I
CP&O
presence of Cu'ci
CI
and HNEt,;["l com10
11
pound 11 forms from
[Cp(Me,P),Ru-C=CH] and [Cp,Zr(CI)(NMe,)] with the elimination of HNMe, ."
The reaction of the rhenium complex 3 with
[(Ph,P),(CO)RhCI] to give 12 is an example of the reaction of
terminal lithiated alkynyl building blocks." 2 ,
I
ON
Li
PPh,
Ph,P-kh-PPh,
I
C
co
3
12
An interesting reaction sequence, which finally leads to complex 16 containing a linear C, bridge, was recently developed by
J. P. Selegue et al.[131
8
7
Ru-C=CH
L'/
+
13
t
TIBF,
*
- TIC1
II
111
C
C
II
I
/
Ph
-cI,I
Ill-
w -CI
C
I
co
LZCP
15
l4
C
Ph
I
co
\ 'L
L
L = PMe,,
P(OMe),
16
9
Transition Metal Complexes with C,, Units (n = 1, 2)
C, Bridges: Complexes with a C , bridge are a rapidly developing class of compounds.[31The C, building blocks can be readily
obtained from acetylene derivatives. Thus, compounds are usually formed in which two identical organometallic substituents
The reaction of the titanium complex 17 with
[CuC=CSiMe,], illustrates that compounds with different
metal complex fragments attached to the C, building block can
also be prepared from (silylalkynyl)
C, Bridges: The elegant synthesis of compound 21 shows that
metal-bound alkynyl groups can be coupled in a way very sim-
HIGHLIGHTS
also be placed on complexes with different terminal transition
metal fragments at the 1,3-butadiyne-l .Cdiyl bridging ligands,[13. 16, 171
17
For the preparation of compounds similar to 27, usually
building blocks are employed which already contain a C, chain.
In this way the coordination of different organometallic terminal groups can be achieved.i161
18
,F e - I
co 1
co
+
-
20
-
+
-I
L
I
I
Fe-CEC-CECH
/:
- Me3Snl
co co
23
ilar to that of free alkynes. Since 20 is chiral, two diastereomers
are formed, which can be separated by crystallization."'. 1 5 ] The
bond lengths in 21 are appropriate for the given formulation of
the complex with two alkyne functions. The dications 22 are
obtained by oxidation of 21; the Re-C and C-C distances in 22
can be assigned to a cumulene system.['51
@
[(Me,CN)PdC&l
Me,Sn-C=C-CECH
24
25
27
26
The preparation of polymers in which the C, building blocks
are linked in a continuous chain as [runs ligands by M L, building blocks is of great interest with regard to new materialsi" ' * ]
The square-planar coordination exhibited by the ds metals (M"
ions) makes them suitable for such linkages. An elegant synthesis for such compounds was described previously by N. Hagihara et al., who showed that [L,Pt(C-C-C=CH),]
reacts with
[L,PdCI,] (L = PBu,) to give the polymer 28.['s1In this way an
ordered series of different metal bridges can be built into the
polymer.
I
C, Chains (n = 1-4) with Terminal Main Group Element Units
+
2 AgPF,
I
I
ON
/I'
Red
\
C
PPh3
!
Red
ON/;\PPh,
II
Polyalkyne derivatives X-C,-Y whose terminal groups X and
Y are main group element units can be prepared by numerous,
in some cases well-developed, procedures." The compounds
29-32 are particularly interesting examples in phosphorus
chemistry.[23- 2 5 1 The chemistry of these compounds has been
intensively studied by the groups of H. J. Bestmann and H.
Schmidbaur.
@
Ph2P--CG
I
8
C-B(CH,Ph),
Me
30
d
8
Ph2P-CZC-C-C-
B(CH2Ph)3
I
Compounds of the type 21 are also known with a range of
other organometallic terminal groups.[31Emphasis here should
A n p i s Clwiii I n f . O I . Engf. 1994. 33, No. 5
Me
32
31
VCH Veriugsjirsribchu~im b H . 0-69451 Weinheim, 1994
0570-0833iY4/O505-0549$ iO.OO+ .25X
549
HIGHLIGHTS
The compounds with C, or C, building blocks can be considered as bis-ylides. Thecompounds with C, or C , building blocks
are zwitterions with charge centers more widely separated from
one another. The preparation of such compounds is exemplified
by the synthesis of 30.[241The structures of 30 and 32 determined
by X-ray analysis support the formulation of the given valence
f o r m ~ I a e . 12 ~
51 ~ .
33
34
c
0
Ph2P-CEC--B(CHzPh)3
35
1
Lie
+
CH31
-
Lil
e
Q
Ph,P--C=C-B(CH,Ph),
I
Me
30
Whereas the preparation of 30 and 32 is relatively simple, the
synthesis of 31 is more difficult. Compound 31 is obtained by
the reaction of the allene-I ,3-diylbisphosphonium salt 36 with
two equivalents of sodium [bis(t~-imethylsilyl)amide].[”~
36
31
Outlook
The isolation of the compounds described reveals that the
highly reactive carbon units C, (n = 1-5) can be stabilized by
suitable terminal building groups. The synthesis of these new
compounds particularly for those containing organometallic
substituents is often surprisingly simple.
The synthesized alkyne complexes offer a fascinating perspective for the preparation of novel organic compounds. In a wider
sense it is also conceivable that alkyne-containing metal complexes with conjugated carbon bridges between different terminal groups could be used as signal transformers in nonlinear
optical materials (NLO) and perhaps even as molecular wires.
Finally, applications in the field of material science may also be
possible in which the inherent mechanical stability of the C,
chains plays an essential role.
German version: An~yeii..Clieni. 1994. 106. 569
[ I ] See for example: a) M . H. Chisholm. A ~ i g r i v .Ciiem. 1991. 103. 690-691:
A n p v . Chiwi. I n l . Ed. Etigi. 1991. 30. 673: h) H. S. Nalua. Appl. Orguiiomef.
(’Iiivii. 1991. 5. 349 ~ 3 7 7 c)
: E Diederich, Y Ruhin, Angeii,. Chrm. 1992. 104.
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d ) G. Frapper. M. Kertesz. Iiiorg. Chem. 1993. 32. 732-740: e ) Y. Zhoii. J. W.
Seyler. W. Weng. A. M. Arif. J. A Gladysz, J. A m Chmi. Soc. 1993. 115.
~509-xsio.
550
1
VCH Ver/ug.~p;est.//.\c/iuff
m h H , D-694.51 Weinlietni, 1994
[2] See for example: a) R. 9. Anderson. The Fi.\c/ier-Eop.w/i ,‘yiir/ifw~, Academic
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(31 W. Beck. 8 . Niemer. M. Wieser. Angerr. C‘llwn. 1993, 105. 969 996. Ang,~etr..
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(‘hem. I n t . Ed. Eng/. 1990. 2Y. 293.
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851-851.
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3x04.
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Oj70-0833~94!0505-11550S 10.00 + .25;0
~
Angru. C/ii*m.I n t . Ed. Engl. 1994, 33. KO.i
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