100113-61-9Relevant academic research and scientific papers
Synthesis, molecular structure, solution dynamics, and reactivity of (η-C5H5)2M(μ-PR2) 2Rh(η-indenyl) (M = Zr, Hf; R = Et, Ph)
Baker,Tulip
, p. 839 - 845 (2008/10/08)
The metal-containing diphosphines , Cp2M(PR2)2 (Cp = η-C5H5; M = Zr, Hf; R = Et, Ph), displace both coordinated ethylenes from (η-C2H4)2Rh(η-indenyl), yielding the early-late heterobimetallic complexes Cp2M(μ-PR2)2Rh(η-indenyl). The molecular structure of Cp2Zr(μ-PPh2)2Rh(η-indenyl) (1c), determined by X-ray diffraction, consists of edge-shared, pseudotetrahedral 16e Zr(IV) and distorted, square-planar Rh(I) centers with a planar ZrP2Rh bridging unit and a Zr?Rh separation of 3.088 (1) A?. The indenyl ligand exhibits a pronounced slip-fold distortion toward η3-coordination and high barriers (14-15 kcal/mol) to indenyl rotation are observed by 1H DNMR. Addition of CH3I to Cp2M(μ-PEt2)2Rh(η-indenyl) affords the cationic d0-d6 heterobimetallics [Cp2M(μ-PEt2)2Rh (CH3)(η-indenyl)]I. Red crystals of 1c are monoclinic, P21/m (no. 11), with two molecules per unit cell of dimensions a = 9.700 (1) A?, b = 18.855 (3) A?, c = 10.185 (1) A?, and β = 112.95 (1)°. The structure was refined to R = 0.029 and Rw = 0.031 for 2928 observed reflections.
