104130-72-5Relevant academic research and scientific papers
Syntheses of secondary-amine-substituted bis(phosphino) molybdenum tetracarbonyl complexes
Tarassoli, Abbas,Chen, Haw-Jan,Thompson, Martin L.,Allured, Viloya S.,Haltiwanger, R. Curtis,Norman, Arlan D.
, p. 4152 - 4157 (2008/10/08)
Reaction of PhN(PCl2)2, PhN[P(NHPh)2]2, or the 1,3,2,4-diazadiphosphetidines [(PhNH)PNPh]3 and [(PhNH)P2(NPh)2]2NPh with norbornadiene-Mo(CO)4 yields the cis complexes PhN(PCl2)2Mo(CO)4 (5), PhN[P(NHPh)2]2Mo(CO)4 (6), [(PhNH)PNPh]3Mo(CO)4 (7), and [(PhNH)P2(NPh)2]2NPhMo(CO)4 (8) in high yields. Reactions of nor-Mo(CO)4 with PhN[P(NHPh)2]2 or a PhN[P(NHPh)2]2-(PhNH)3P mixture or (PCl3)2Mo(CO)4 with PhNH2/Et3N yields 6 quantitatively in reactions that involve metal-templated P-N bond condensation reactions. 5 reacts with PhNH2/Et3N or i-PrNH2/Et3N to form 6 or i-PrN[(i-PrNH)3(PhNH)P2]Mo(CO)4 (9), respectively. 6 has been characterized structurally by single-crystal X-ray crystallography. Crystals of 6-1/2C6H6 are hexagonal, space group P6122, with a = 15.604 (4) ?, b = 15.604 (4) ?, c = 28.712 (4) ?, and Z = 6. The structure, solved by direct methods, refined to R = 0.074 and Rw = 0.085 for 539 observed reflections. The complex is a bis(phosphino)amino complex in which phosphorus atoms are coordinated to cis positions of the Mo(CO)4 moiety. Comparison of physical and spectral properties of 5, 7, 8, and 9 with those of 6 allows the former compounds to be characterized as bis(phosphino)amine complexes. In every case bis(phosphino) phosphorus coordination to the Mo(CO)4 moiety occurs; no evidence for 1,3,2,4-diazadiphosphetidine terminal phosphorus or ring coordination is seen. Reaction of cis-(PhNPCl)2 or cis-[(PhNH)PNPh]2 with nor-Mo(CO)4 yields intractable products.
