Formation of [Rh(CO)Cl{P(C6H5)3}2] from [RhCl{P(C6H5)3}3] and carbon dioxide

Svoboda, P.; Hetflejš, J.

doi:10.1135/cccc19751746

Cited by 16 publications

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“…This conclusion seems to hold true in a more general sense as indicated by the following observations. If one generates in a chemical ionization source the "mixed" complex Fe+(CH3NC) (CD3CN), the only product observed8 in the MI spectrum of this mass-selected species is due to the loss of CD3CN proving13 that BE(Fe+- (5) Czekay, G.; Drewello, T.; Eller, K.; Zummack, W.; Schwarz, H. Organometallics, in press. (6) Stepnowski, R. M.; Allison, J. Organometallics 1988, 7, 2097.…”

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The detailed mechanism for the reaction of bare iron(I) ions with tert-butyl cyanide and isocyanide in the gas phase

Eller¹,

Schwarz²

1989

Organometallics

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Experimental evidence is presented demonstrating that bare Fe+ does not insert in the C-X bond of (CH,),C-X (X = CN, NC). Rather, initial "end-on" complexation of the functional group induces cleavage of this bond which is followed by hydrogen transfer to X; this results in the formation of diligated complexes of the general structure C,H,-.M+-.XH (Scheme 111, 9 and 12). These intermediates serve as precursors for the competitive loss of C, H, and HX; by means of high-energy collisional activation the products due to the unimolecular elimination of C4H, are characterized by MS/MS techniques as the "end-on" complexes of HCN and HNC with Fe' (10 and 13, respectively). Moreover, new insight into the mechanism of "dissociative attachment" is provided.

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confidence: 99%