The reactions of cationic carbyne complexes of manganese and rhenium, [η-C 5 H 5 (CO) 2 Mt CC 6 H 5 ]BBr 4 (1, M ) Mn; 2, M ) Re), with Na[η-C 5 H 5 Mo(CO) 3 ] (3) in THF at low temperature afford η 1 ,η 2 -ketene complexes [MnMo{C(CO)C 6 H 5 }(CO) 4 (η-C 5 H 5 ) 2 ] (8) and [ReMo{C(CO)-C 6 H 5 }(CO) 4 (η-C 5 H 5 ) 2 ] (9), respectively. Analogous reactions of Na[η-C 5 H 5 W(CO) 3 ] (4) with 1 and 2 give the corresponding ketene complexes [MnW{C(CO)C 6 H 5 }(CO) 4 (η-C 5 H 5 ) 2 ] (10) and [ReW{C(CO)C 6 H 5 }(CO) 4 (η-C 5 H 5 ) 2 ] (11). Na[Co(CO) 3 PPh 3 ] (5) also reacts with 1 and 2 to yield ketenyl-bridged complexes [MnCo{C(CO)C 6 H 5 }(CO) 4 (PPh 3 )(η-C 5 H 5 )] ( 12) and [ReCo{C(CO)-C 6 H 5 }(CO) 4 (PPh 3 )(η-C 5 H 5 )] (13), respectively. However, compound Na[η-C 5 H 5 Fe(CO) 2 ] (6) reacts only with 2 to form a η 1 ,η 2 -ketene complex [ReFe{C(CO)C 6 H 5 }(CO) 3 (η-C 5 H 5 ) 2 ] (14), while the reactions of (Ph 3 P) 2 N[Fe(CO) 3 NO] ( 7) with 1 and 2 produce dimetal bridging carbyne complexes [MnFe(µ-CC 6 H 5 )(CO) 4 (NO)(η-C 5 H 5 )] ( 15) and [ReFe(µ-CC 6 H 5 )(CO) 4 (NO)-(η-C 5 H 5 )] ( 16), respectively. Compound 15 treated with an excess of Fe 2 (CO) 9 gives a trimetallic bridging carbyne complex, [MnFe 2 (µ 3 -CC 6 H 5 )(CO) 7 (NO)(η-C 5 H 5 )] (17). Complexes 12 and 13 also react with Fe 2 (CO) 9 , leading to loss of the PPh 3 ligand to afford trimetallic bridging carbyne complexes [MnFeCo(µ 3 -CC 6 H 5 )(CO) 8 (η-C 5 H 5 )] ( 18) and [ReFeCo(µ 3 -CC 6 H 5 )-(CO) 8 (η-C 5 H 5 )] ( 19), respectively. The structures of 10, 13, and 15 have been established by X-ray diffraction studies.
The reaction of a cationic carbyne complex of manganese, [η-C5H5(CO)2Mn⋮CC6H5]BBr4
(1), with (Ph3P)2NW(CO)5NCO (3) in THF at low temperature gave the novel chelated carbene
complex [η-C5H4(CO)2MnC(NHCO)C6H5] (6). The analogous reaction of a cationic carbyne
complex of rhenium, [η-C5H5(CO)2Re⋮CC6H5]BBr4 (2), with 3 afforded the azametallacyclic
complex [η-C5H5(CO)2ReC(C6H5)(CO)NW(CO)5] (7). The reaction between 1 and (Ph3P)2NW(CO)5SCN (4) led to the loss of a sulfur atom to give the phenyl(pentacarbonylisocyanotungsten)carbene−manganese complex [η-C5H5(CO)2MnC(C6H5)CNW(CO)5] (8). However,
the reaction of 2 with 4 afforded the (isothiocyanato)phenylcarbene−rhenium complex
[η-C5H5(CO)2ReC(C6H5)SCN] (9). Complexes 1 and 2 react with NaW(CO)5CN (5) to produce
novel phenyl(pentacarbonylcyanotungsten)carbene−manganese and −rhenium complexes,
[η-C5H5(CO)2MnC(C6H5)NCW(CO)5] (10) and [η-C5H5(CO)2ReC(C6H5)NCW(CO)5] (11),
respectively. The structures of 6, 7, 8, and 11 have been established by X-ray diffraction
studies.
The reaction of a cationic carbyne complex of manganese,
[η-C5H5(CO)2Mn⋮CC6H5]BBr4
(1), with
(Ph3P)2NFeCo(CO)8
(3) in THF at low temperature gave a heteronuclear
dimetal
bridging carbyne complex
[MnCo(μ-CC6H5)(CO)5(η-C5H5)]
(5) and a bridging carbene complex
[MnCo{μ-C(CO)C6H5}(CO)5(η-C5H5)]
(6).
Ph3P)2NWCo(CO)9
(4) also reacted with 1 to give
the same products 5 and 6. The analogous
reaction of the cationic carbyne complex of
rhenium,
[η-C5H5(CO)2Re⋮CC6H5]BBr4
(2), with 3 or 4 afforded the
corresponding bridging
carbyne complex
[ReCo(μ-CC6H5)(CO)5(η-C5H5)]
(7) and bridging carbene complex
[ReCo{μ-C(CO)C6H5}(CO)5(η-C5H5)]
(8). 5 can convert to 6 by
reaction with carbon monoxide gas. 5
or 6 reacted with Fe2(CO)9 to
afford a trimetal bridging carbyne complex
[MnFeCo(μ3-CC6H5)(μ-CO)(CO)7(η-C5H5)]
(9). Analogous reaction of 7 or 8
with Fe2(CO)9 yielded the
trimetal
bridging carbyne complex
[ReFeCo(μ3-CC6H5)(CO)8(η-C5H5)]
(10). The structures of 5, 7,
8,
9 and 10 have been established by X-ray
diffraction studies.
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