The Effect of One Valence Electron: Contrasting (PNP)Ni(CO) with (PNP)Ni(NO) to Understand the Half-Bent NiNO Unit.

The Effect of One Valence Electron: Contrasting (PNP)Ni(CO) with (PNP)Ni(NO) to Understand the Half-Bent NiNO Unit. Research Abstract Details 

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The Effect of One Valence Electron: Contrasting (PNP)Ni(CO) with (PNP)Ni(NO) to Understand the Half-Bent NiNO Unit. Abstract Text:

Reaction of a (PNP)Ni radical with NO finishes in the time of mixing to form a 1:1 adduct with a NO stretching frequency of 1654 cm (-1). NMR data of this diamagnetic product indicate C 2 v symmetry, which is contradicted by the X-ray structure, which shows it to be nonplanar at Ni, with a geometry intermediate between planar and tetrahedral; the planar geometry is thus the transition state for fluxionality giving time-averaged C 2 v symmetry. The X-ray structure, together with DFT calculations, reveals that the "half-bent" NiNO unit and the intermediate coordination geometry result from a Ni --> NO charge transfer, which has a nonintegral value, resulting in a continuum between NO (+) (hence Ni (0)) and NO (-) (hence Ni (II)). This is related to the nonaxially symmetric character of the Ni --> NO back-donation caused by the (PNP) environment on Ni. Steric effects of ( t )Bu and even chelate constraints are ruled out as the cause of the unusual electronic and structural features.

The Effect of One Valence Electron: Contrasting (PNP)Ni(CO) with (PNP)Ni(NO) to Understand the Half-Bent NiNO Unit. Publishing Authors By Initials

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The Effect of One Valence Electron: Contrasting (PNP)Ni(CO) with (PNP)Ni(NO) to Understand the Half-Bent NiNO Unit. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Inorganic chemistry

VOLUME: 47

Page Numbers: 3888-92

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ISSN: 0020-1669

DAY: 21

MONTH: 03

YEAR: 2008

The Effect of One Valence Electron: Contrasting (PNP)Ni(CO) with (PNP)Ni(NO) to Understand the Half-Bent NiNO Unit. Information

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LANGUAGE: eng

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AFFILIATION: caulton@indiana.edu.

Country: United States

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MEDLINETA: Inorg Chem

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