89321-53-9Relevant academic research and scientific papers
Oxidative addition of dimethylthiocarbamoyl chloride to [Rh2Cl2(μ-CO)(Ph2PCH2PPh 2)2], the facile interconversion between chelating η2 and bridging coordination modes of the SCNMe2 group, and the structure of [Rh2Cl2(CO)(SCNMe2)(Ph ...
Gibson, John A. E.,Cowie, Martin
, p. 722 - 731 (2008/10/08)
Full title: Oxidative addition of dimethylthiocarbamoyl chloride to [Rh2Cl2(μ-CO)(Ph2PCH2PPh 2)2], the facile interconversion between chelating η2 and bridging coordination modes of the SCNMe2 group, and the structure of [Rh2Cl2(CO)(SCNMe2)(Ph2PCH 2PPh2)2][BF4]·1.833CH 2Cl2. Oxidative addition of SC(Cl)NMe2 to [Rh2Cl2(μ-CO)(DPM)2] (1) (DPM = Ph2PCH2PPh2) yields [Rh2Cl3(CO)(SCNMe2)(DPM)2] (2). In the presence of BF4- the product of oxidative addition is [Rh2Cl2(CO)(SCNMe2)(DPM)2][BF 4] (3). An X-ray structure determination of 3 (space group P21/n, a = 12.340 (1) A?, b = 32.888 (5) A?, c = 15.374 (2) A?, β = 105.935 (8)°, Z = 4) shows that the SCNMe2 moiety is bound in an η2 fashion to one metal center. This structure has refined to R = 0.070 and Rw = 0.081 for 4122 observations and 345 parameters varied. The reaction of 3 with Me3NO results in CO loss, yielding [Rh2Cl2(μ-SCNMe2)(DPM)2][BF 4] (4) in which the SCNMe2 group bridges the two metals. Compound 4 reacts with CO to regenerate 3 and reacts with methyl isocyanide to give the analogous isocyanide compound, [Rh2Cl2(CNMe)(SCNMe2)(DPM)2][BF 4] (5). The reduction of compound 3 employing BH4- was carried out to give the very air-sensitive species [Rh2(CO)(μ-SCNMe2)(solvent)(DPM)2] [BF4] (solvent = THF (6a), acetonitrile (6b)). Compounds 6a and 6b react with CO to give [Rh2(CO)2(μ-SCNMe2)-(DPM) 2][BF4] (7). 0276-7333/84/2303-0722$01.50/0
