Cooligomerization of Phosphaalkynes and Alkynes in the Coordination Sphere of Rhodium Complexes

Phospha-alkyne hydro-osmiation: synthesis of [Os{κ1P,κ1P′-PCRP(CHR)}Cl(CO)(PPh3)2] (R = CMe3)

“…[Os{PNC(CF 3 )O}(CO) 2 (PPh 3 ) 2 ], 9 [Rh{PNC(CMe 3 )-CNCH 2 }Cl(PPr i 3 ) 2 ], 10 and the l 5 -phospha-alkenyl complex [Ru{P(NO)NC(CMe 3 )C(NO)}(CNCMe 3 ) 2 (PPh 3 ) 2 ], 11 (spectroscopic data of which support our formulation). The route by which 4 is formed presumably involves a slow insertion of one equivalent of P•CCMe 3 into the osmium hydride bond to provide transiently the phospha-alkenyl complex [Os(PNCHC-Me 3 )Cl(CO)(PPh 3 ) 2 ], followed by a rapid insertion of a second equivalent of phospha-alkyne into the Os-P bond and subsequent metallacyclisation.…”

Phosphaalkyne Hydrometalation: Synthesis and Reactivity of the Complexes [Ru(PCHCMe3)Cl(CA)(PPh3)2] (A = O, S)

“…In the intervening years since Roper's report of the first example of a metallacyclic phosphaalkenyl complex, 33 very few ex-amples have since emerged and all involve twocoordinate λ 3 -phosphorus. 34,35 The complex 10 which contains two isocyanide ligands clearly results from a disproportionation involving loss of isocyanide from 4a and coordination of this to a second molecule of 4a. This is supported by the observation that 5(Cl) is also decomposed slowly by air to provide 10.…”

A metallacyclic λ5-phosphaalkenyl complex of ruthenium(II): X-ray structure of [Ru{κ2-P(O)CButC(O)}(CNBut)2(PPh3)2]

“…8 The chemistry of l 3 phosphaalkenyl ligands has seen substantial growth in recent times. [1][2][3][4][5][6]9 With the advent of a l 5 example, it will be interesting to see how their respective coordination chemistries compare.…”