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• W2113123503 abstract "Abstract A synthetic methodology to obtain square‐planar carbenerhodium(I) complexes of the general composition trans ‐[RhCl(CRR′)(L) 2 ] where L is a tertiary phosphane, arsane, or stibane has been developed. The starting material trans ‐[RhCl(C 2 H 4 )(Sb i Pr 3 ) 2 ] ( 3 ) reacts with diazoalkanes RR′CN 2 [RR′ = Ph 2 , Ph(C 6 H 4 X), (C 6 H 4 X) 2 , Ph(CF 3 ), C 12 H 8 ] under mild conditions to give the compounds trans ‐[RhCl(CRR′)(Sb i Pr 3 ) 2 ] ( 4–11 ) almost quantitatively. On treatment of 3 with EtO 2 CCHN 2 and PhC(N 2 )C(O)R, the olefinrhodium and diazoalkanerhodium compounds trans ‐[RhCl{( E )‐C 2 H 2 (CO 2 Et) 2 }(Sb i Pr 3 ) 2 ] ( 12 ) and trans ‐[RhCl{N 2 C(R)C(O)Ph}(Sb i Pr 3 ) 2 ] ( 13, 14 ) are obtained instead of carbene complexes. Displacement of the Sb i Pr 3 ligands in 4 (R = R′ = Ph) by P i Pr 3 , P i Pr 2 Ph, P i PrPh 2 , PPh 3 , PPh 2 Me, As i Pr 3 , and SbEt 3 leads to the corresponding carbene complexes trans ‐[RhCl‐(CPh 2 )(L) 2 ] ( 15–21 ) in high yields. The results of the X‐ray crystal structure analyses of 4 and 15 (L = P i Pr 3 ) illustrate that the different donor—acceptor properties of Sb i Pr 3 and P i Pr 3 have little influence on the RhC bond length. The reactions of 4 and 15 with CO and CN t Bu afford, by metal‐assisted CC coupling, diphenylketene Ph 2 CCO ( 23 ) and the corresponding imine Ph 2 CCN t Bu ( 26 ). On treatment of 4 and 15 with ethene, however, two different olefinic products, 3,3‐diphenyl‐1‐propene ( 31 ) and 1,1‐diphenyl‐1‐propene ( 32 ), are formed. Compound 15 reacts with KBr, NaOPh, and NaC 5 H 5 by substitution of the chloride to give trans ‐[RhBr(CPh 2 )‐(P i Pr 3 ) 2 ] ( 33 ), trans ‐[Rh(OPh)(CPh 2 )‐(P i Pr 3 ) 2 ] ( 34 ) and [C 5 H 5 Rh(CPh 2 )‐(P i Pr 3 )] ( 35 ), and with HCl by oxidative addition to yield [RhCl 2 (CHPh 2 )‐(P i Pr 3 ) 2 ]( 36 )." @default.
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• W2113123503 date "1997-08-01" @default.
• W2113123503 modified "2023-10-17" @default.
• W2113123503 title "A New Family of Carbenerhodium(I) Complexes: Ligand Variation as The Key to Success" @default.
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• W2113123503 doi "https://doi.org/10.1002/chem.19970030826" @default.
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