Reactivity of the metal-metal multiple bond in metalcarbonyl derivatives. 11. Reaction of (C5H5)2Mo2(CO)4 with carbodiimides: structural characterization of C5H5(CO)2Mo(CNPh)Mo(NPh)C5H5, a novel complex containing a terminal phenylimido and a bridging phenyl isocyanide ligand, and its reaction with P(OMe)3

Abstract

Supplementary Material Available: Listings of anisotropic thermal parameters, complete bond distances and bond angles, and final observed and calculated structure factors (22 pages). Ordering information is given on any current masthead page.

Reactions of Cyclohexyl Isocyanide with η5‐Substituted Cyclo‐pentadienyl MoMo Triply Bonded Complexes. Crystal Structure of [Mo(CO)2(η5‐C5H4CO2CH3)]2(μ‐η2‐CNC6H11)

“…However, in the case with a smaller steric hindrance situation, the isocyanide favors as a bridging ligand (Figure 1b and 1c), in which the C≡N bond lengths are longer and the ∠Mo1-C-N and ∠C-N-R are smaller than those in the above mentioned terminally coordinated complexes shown in Figure 1a, such as in complexes Mo 2 (CO) 4 (C 5 Me 5 ) 2 (CF 3 NC), 19 Mo 2 (CO) 4 -(C 5 Me 5 ) 2 (CF 3 CH 2 NC) 20 ( Figure 1b), and in complexes Mo 2 (CO) 4 (C 5 H 5 ) 2 (PhNC), 11,21 Mo 2 (CO) 4 (C 5 Me 5 ) 2 -(CH 3 NC), 22 Mo 2 (CO) 4 (C 5 H 5 ) 2 (t-BuNC), 12 Mo 2 (CO) 3 -(C 5 H 5 ) 2 (dppm)(t-BuNC), 23 and Mo 2 (CO) 2 (C 5 H 5 ) 2 (NPh)-(PhNC) (Figure 1c). 24 In addition, the ν (N≡C) values in these complexes are in the range 1600-1750 cm -1 . It follows that the isocyanide coordination modes in complexes 1a, 1b and 2a, 2b appear to be the coordination modes shown in Figure 1c and 1a, respectively.…”