Abstract
Reaction of Na[Co(CO) 4 ] with [Cp 2 Fe 2 (CO) 2 (μ-CO)Gu-CSMe)]PF 6 , 1a, under UV photolysis gives a high yield of Cp 2 Fe 2 Co(CO) 3 (μ-CO) 2 )(μ-CSMe), 2a. A single-crystal X-ray diffraction study of 2a shows that it crystallizes in the monoclinic cell P2 1 /c with a = 7.057 (1) Å, b = 14.767 (2) Å, c = 17.674 (3) Å, and β = 99.86 (3)° and four molecules per unit cell. The structure was refined to R = 0.044 and R w = 0.051 for the 2942 observed reflections with I(obsd) ≥ 3 σI. The cluster has an L-shaped triangular structure, but there is no Co-Fe bond on one edge of the triangle. The CSMe group bonds through the carbyne carbon to all three metals, and in addition, the sulfur coordinates to the cobalt atom. Compound 2a reacts with phosphines (PPh 8 , PEt 3 , PCy 3 , PHPh 2 , PMePh 2 , Ph 2 PCH 2 PPh 2 ) to substitute a CO on cobalt. A single-crystal X-ray diffraction study of the PPh 3 derivative Cp 2 Fe 2 Co(CO) 2 (PPh 3 )(μ-CO) 2 (μ 3 -CSMe), 3a, shows that it crystallizes in the monoclinic cell P2 1 /n with a = 13.388 (3) Å, b = 23.188 (6) Å, c = 10.126 (2) Å, and β = 100.11 (2)° and four molecules per unit cell. The structure was refined to R = 0.067 and R w = 0.068 for the 2127 observed reflections with I(obsd) ≥ 3σI. Compound 3a has the same basic structure as 2a except that a CO on Co is substituted by PPh 3 . Compound 2a reacts with HBF 4 •Et 2 O and with oxidants (Ag + , Ph 3 C + , I 2 , NOPF 6 ) to yield 1a. IR and 1 H NMR spectra of the complexes are also reported and discussed. © 1985, American Chemical Society. All rights reserved.