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• W1973051984 startingPage "10189" @default.
• W1973051984 abstract "Magnesium reduction of cis,cis,trans-RuCl2(CO)2L2 (L = PtBu2Me) yields isolable Ru(CO)2L2, shown by solution spectroscopies and X-ray diffraction to have trans phosphines but cis carbonyls, in a nonplanar structure which resembles a trigonal bipyramid with one equatorial ligand missing. This unusual geometric structure is traced by ab initio (MP2) study to enhanced back-donation to CO by zero-valent Ru. This molecule reacts in time of mixing to add CO, MeNC, O2, CS2, C2H4, or PhC⋮CPh. Rapid oxidative addition occurs with H2, HCl, Cl2, and PhC⋮CH. Oxidative addition is slower with MeCl, Me3SiH, and MeOH, which leads to more complicated reaction schemes. Reaction with PPh2H gives not oxidative addition but addition and displacement, yielding Ru(CO)2(PPh2H)2(PtBu2Me) and equimolar free PtBu2Me. Magnesium reduction of cis,cis,trans-RuCl2(CO)2L‘2 proceeds analogously for L‘ = PiPr3, but for L‘ = PPh3, decomposition and ligand scavenging give Ru(CO)2(PPh3)3. Reduction of cis,trans-RuCl2(CO)(CNMe)L2 gives the product of oxidative addition of a tBu C−H bond: RuH(CO)(CNMe)[η2-P(CMe2CH2)tBuMe]L, showing the influence of electron density at unsaturated Ru(0) on its persistence." @default.
• W1973051984 created "2016-06-24" @default.
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• W1973051984 date "1996-01-01" @default.
• W1973051984 modified "2023-10-16" @default.
• W1973051984 title "Characterization and Reactivity of an Unprecedented Unsaturated Zero-Valent Ruthenium Species: Isolable, Yet Highly Reactive" @default.
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• W1973051984 doi "https://doi.org/10.1021/ja960967w" @default.
• W1973051984 hasPublicationYear "1996" @default.
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