Multifunctional behavior by a Bis-(phosphinimino)methanide ligand: eta 2- vs eta 3-coordination vs Bronsted basicity.

Multifunctional behavior by a Bis-(phosphinimino)methanide ligand: eta 2- vs eta 3-coordination vs Bronsted basicity. Research Abstract Details 

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Multifunctional behavior by a Bis-(phosphinimino)methanide ligand: eta 2- vs eta 3-coordination vs Bronsted basicity. Abstract Text:

Christine Bibal,Maren Pink,Yegor D Smurnyy,John Tomaszewski,Kenneth G Caulton,

The reaction of [(Cymene)RuCl2]2 with the chelate LiHC(PPh2NPh)2 occurs to remove both chloride ligands, to furnish a cationic Ru(II) complex with the monoanionic ligand bound eta3, through two N and an sp3 carbon. This cation is also produced from the conjugate acid of the ligand H2C(PPh2NPh)2 because this molecule can serve as a Brønsted base, to deprotonate the acidic carbon of another molecule of H2C(PPh2NPh)2. DFT calculations show an energy surface where (Cymene)RuHC(PPh2NPh)2L is more stable with a Ru-CH(PPh2NPh)2 bond and with L = Cl- or MeCN not coordinated to Ru, than to an eta2-HC(PPh2NPh)2 structure with coordinated L; this is tested experimentally. The greater tendency for this ligand to be coordinated eta3 vs analogous diketiminates is discussed. The nucleophilicity of Cgamma in structure 1, vs that of donors L = Cl- or MeCN, is evaluated to understand the preference of the bis(phosphinimino)methanide to be bidentate or tridentate.

Multifunctional behavior by a Bis-(phosphinimino)methanide ligand: eta 2- vs eta 3-coordination vs Bronsted basicity. Publishing Authors By Initials

C Bibal,M Pink,YD Smurnyy,J Tomaszewski,KG Caulton,

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Multifunctional behavior by a Bis-(phosphinimino)methanide ligand: eta 2- vs eta 3-coordination vs Bronsted basicity. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Journal of the American Chemical Society

VOLUME: 126

Page Numbers: 2312-3

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 3

MONTH: Mar

YEAR: 2004

Multifunctional behavior by a Bis-(phosphinimino)methanide ligand: eta 2- vs eta 3-coordination vs Bronsted basicity. Information

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LANGUAGE: eng

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AFFILIATION: Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.

Country: United States

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MEDLINETA: J Am Chem Soc

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