112654-40-7Relevant academic research and scientific papers
Dinuclear homo- and heterometallic rhodium complexes containing PMe2 and PPh2 groups as bridging ligands. The crystal and molecular structure of [(C5Me5Rh)2(μ-PMe2)(μ-PPh 2)]
Werner, Helmut,Klingert, Bernd,Rheingold, Arnold L.
, p. 911 - 917 (2008/10/08)
The reaction of [C5Me5Rh(PMe2H)Cl2] (4), which is prepared from [C5Me5RhCl2]2 (2) and PMe2H, with excess diethylamine, produces a mixture of [C5Me5(Cl)Rh(μ-PMe2)]2 (6), [C5Me5Rh(PMe2NEt2)Cl2] (7), and [C5Me5Rh(μ-PMe2)]2 (9). 7 reacts with HF (in pyridine) and with HCl (in benzene) to form the complexes [C5Me5Rh(PMe2F)Cl2] (8) and [C5Me5Rh(PMe2Cl)Cl2] (10), respectively, the latter of which is reduced with sodium amalgam to give 9. Compound 9 is also obtained by reduction of 6 with Na-Hg. Treatment of [C5Me5Rh(PPh2H)Cl2] (11) with excess NEt2H leads to the formation of [C5Me5Rh(μ-PPh2)]2 (13) and [(C5Me5Rh)2(μ-PPh2)(μ-Cl)] (14). The structurally related complexes [(C5Me5Rh)2(μ-PMe2)(μ-PPh 2)] (15) and [(C5Me5Rh)2(μ-PPh2)(μ-SMe)] (16) have been prepared from 14 by bridge-ligand exchange. The crystal and molecular structure of 15 have been determined. For C34H46P2Rh2 (15): triclinic, P1; a = 10.053 (3), b = 11.271 (4), c = 16.761 (4) A?; α = 93.32 (2)°, β= 85.78 (2)°, γ = 116.45 (2)°; V = 1694.8 (6) A?3; Z = 4; for 4938 observed reflections, RF = 3.39%. 15 contains a folded butterfly Rh2P2 core with a 111.5 (2)° core dihedral angle and a Rh-Rh bond of 2.7952 (4) A?. The synthesis of the dinuclear homo- and heterometallic complexes [C5Me5Rh(μ-PMe2)2MC 5H5] (17, M = Rh; 18, M = Co) and [C5Me5Rh(μ-PMe2)2RuC 6H6] (19) has been achieved starting from [C5Me5Rh(PMe2H)2], CH3Li, and [C5H5M(CO)I2] or [C6H6RuCl2]2, respectively.
