The X-ray structural analysis of the compound [(pp3)Nil]BPh4 (complex d), pp3 = P(CH2CH2PPh2)3, is presented. The complex cation has an almost regular trigonal bipyramidal geometry (TBP) with distances Ni-I and Ni-Pax of 2.546(2) and 2.142(3) Å, respectively. This structure completes a series of strictly related nickel complexes, namely [(np3)Nil]I, complex a; (np3)Nil, complex b; (np3)Ni, complex c; [(pp3)NiHClO4), complex e; [np3 = N(CH2CH2PPh2)3] The complexes are redox derivatives [Ni(II), Ni(I), Ni(O)] that can be isolated via chemistry and/or electrochemistry. In the solid state complexes c and e have a trigonal pyramidal (TP) structure, whereas, electrochemical measurements suggest that in solution the TBP structure with a very elongated Ni-I bond can also have a finite lifetime. EHMO calculations offer a satisfying interpretation of the main structural trends in complexes a rarr e, in particular, those relative to axial bond stretching, and clarify the different roles of phosphine vs. the amine axial donor. Moreover, the correlation is discussed between the electrode potentials and the nature of the Ni-I sgr* MO that accepts or releases the electrons exceeding thed 8 configuration of Ni(II).

Stepwise electron-induced demolition of the Ni-I sigma-bond in complexes with tetradentate tripodal ligands: A theoretical rationalization of structural and electrochemical results / C.A. Ghilardi, C. Mealli, S. Midollini, A. Orlandini, D.M. Proserpio, A. Cinquantini, P. Zanello. - In: STRUCTURAL CHEMISTRY. - ISSN 1040-0400. - 1:5(1990), pp. 441-454.

Stepwise electron-induced demolition of the Ni-I sigma-bond in complexes with tetradentate tripodal ligands: A theoretical rationalization of structural and electrochemical results

D.M. Proserpio;
1990

Abstract

The X-ray structural analysis of the compound [(pp3)Nil]BPh4 (complex d), pp3 = P(CH2CH2PPh2)3, is presented. The complex cation has an almost regular trigonal bipyramidal geometry (TBP) with distances Ni-I and Ni-Pax of 2.546(2) and 2.142(3) Å, respectively. This structure completes a series of strictly related nickel complexes, namely [(np3)Nil]I, complex a; (np3)Nil, complex b; (np3)Ni, complex c; [(pp3)NiHClO4), complex e; [np3 = N(CH2CH2PPh2)3] The complexes are redox derivatives [Ni(II), Ni(I), Ni(O)] that can be isolated via chemistry and/or electrochemistry. In the solid state complexes c and e have a trigonal pyramidal (TP) structure, whereas, electrochemical measurements suggest that in solution the TBP structure with a very elongated Ni-I bond can also have a finite lifetime. EHMO calculations offer a satisfying interpretation of the main structural trends in complexes a rarr e, in particular, those relative to axial bond stretching, and clarify the different roles of phosphine vs. the amine axial donor. Moreover, the correlation is discussed between the electrode potentials and the nature of the Ni-I sgr* MO that accepts or releases the electrons exceeding thed 8 configuration of Ni(II).
Settore CHIM/03 - Chimica Generale e Inorganica
1990
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/206456
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