Influence of the d-Electron Count on CO Binding by Three-Coordinate [((t)Bu(2)PCH(2)SiMe(2))(2)N]Fe, -Co, and -Ni.

Influence of the d-Electron Count on CO Binding by Three-Coordinate [((t)Bu(2)PCH(2)SiMe(2))(2)N]Fe, -Co, and -Ni. Research Abstract Details 

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Influence of the d-Electron Count on CO Binding by Three-Coordinate [((t)Bu(2)PCH(2)SiMe(2))(2)N]Fe, -Co, and -Ni. Abstract Text:

Michael J Ingleson,Benjamin C Fullmer,Drew T Buschhorn,Hongjun Fan,Maren Pink,John C Huffman,Kenneth G Caulton,Michael J Ingleson,Benjamin C Fullmer,Drew T Buschhorn,Hongjun Fan,Maren Pink,John C Huffman,Kenneth G Caulton,Michael J Ingleson,Benjamin C Fullmer,Drew T Buschhorn,Hongjun Fan,Maren Pink,John C Huffman,Kenneth G Caulton,

Reduction of (PNP)MCl [PNP = (tBu2PCH2SiMe2)2N] with Mg gives three-coordinate, T-shaped (PNP)M for M = Fe(S = 3/2) and Ni. Their reactivity was tested toward CO; Ni binds one CO, but only reversibly (i.e., CO is completely lost in vacuum), and has a CO stretching frequency showing effective back-donation by NiI. The structure of (PNP)Ni(CO) is intermediate between planar and tetrahedral, in contrast to the planar d8 analogue, (PNP)Co(CO). This structural reorganization on carbonylation changes the singly occupied molecular orbital from having negligible phosphorus character [no P hyperfine structure in the electron paramagnetic resonance (EPR) spectrum of (PNP)Ni] to having enough P character to have a triplet structure in the EPR spectrum of the CO. The presence of one fewer electron in (PNP)Fe (vs the Co analogue) leads to binding of two CO, and (PNP)Fe(CO)2 is characterized as a spin doublet with square-pyramidal structure. Density functional theory calculations strengthen the understanding of the structural and spectroscopic changes along this dn series (n = 7-9).

Influence of the d-Electron Count on CO Binding by Three-Coordinate [((t)Bu(2)PCH(2)SiMe(2))(2)N]Fe, -Co, and -Ni. Publishing Authors By Initials

MJ Ingleson,BC Fullmer,DT Buschhorn,H Fan,M Pink,JC Huffman,KG Caulton,MJ Ingleson,BC Fullmer,DT Buschhorn,H Fan,M Pink,JC Huffman,KG Caulton,MJ Ingleson,BC Fullmer,DT Buschhorn,H Fan,M Pink,JC Huffman,KG Caulton,

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Influence of the d-Electron Count on CO Binding by Three-Coordinate [((t)Bu(2)PCH(2)SiMe(2))(2)N]Fe, -Co, and -Ni. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Inorganic chemistry

VOLUME: 47

Page Numbers: 407-9

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ISSN: 0020-1669

DAY: 23

MONTH: 12

YEAR: 2007

Influence of the d-Electron Count on CO Binding by Three-Coordinate [((t)Bu(2)PCH(2)SiMe(2))(2)N]Fe, -Co, and -Ni. Information

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LANGUAGE: eng

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Grant and Affiliation Information for Influence of the d-Electron Count on CO Binding by Three-Coordinate [((t)Bu(2)PCH(2)SiMe(2))(2)N]Fe, -Co, and -Ni.

AFFILIATION: Department of Chemistry, Indiana University, Bloomington, Indiana 47405.

Country: United States

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MEDLINETA: Inorg Chem

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