194302-24-4Relevant academic research and scientific papers
2-phosphanylphosphinines as bridging ligands for dinuclear transition metal carbonyls
Waschbuesch, Klaus,Floch, Pascal Lc,Ricard, Louis,Mathey, Francois
, p. 843 - 849 (2007/10/03)
The 2-phosphanyl-4,5-dimethylphosphinines 1-5 are powerful bridging ligands able to stabilize metal-metal single and triple bonds between low-valent transition metal centres. Their reaction with Mn2(CO)10 in refluxing xylene yields the corresponding Mn2(CO)8 complexes 6 and 7. Reaction with [Fe2Cp2(CO)4] under UV irradiation similarly yields the Fe-Fe-bridged Fe2Cp2(CO)2 complexes 8 and 9. An additional observation is that the 2-phosphininyl-3,4-dimethylphosphaferrocene 10 is formed upon reaction of the 2-phospholylphosphinine 5 with [Fe2Cp2(CO)4] at high temperature under CO pressure. A clean addition occurs at the Mo=Mo triple bond of [Mo2Cp2(CO)4] to give the Mo-Mo single-bonded complexes 11 -15. The thermolysis of these complexes succeeds when the phosphanyl group is a phosphonite P(OEt)2 (13) or P(OAr)2 (14), affording cleanly the Mo2Cp2(CO)2 triple-bonded complexes 16 and 17, respectively. The metalmetal triple bonds of these complexes readily add two molecules of CO to reform 13 and 14, or one molecule of tBu-N≡C to give 18 and 19. The X-ray crystal structure analysis of the Mo2Cp2(CO)4 complex 13a, with the 2-P(OEt)2phosphinine, shows a gauche orientation of the two Cp rings and very short P-Mo bonds of 2.3565(4) and 2.406(2) A to the phosphinine and P(OEt)2 groups, respectively. VCH Verlagsgesellschaft mbH,.
