Multifunctional Behavior by a Bis-(phosphinimino)methanide Ligand: η2-vs η3-coordination vs Bronsted Basicity

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

doi:10.1021/ja039711y

Multifunctional Behavior by a Bis-(phosphinimino)methanide Ligand: η²-vs η³-coordination vs Bronsted Basicity

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

Department of Pathology and Anatomical Sciences

University at Buffalo

Research output: Contribution to journal › Article › peer-review

33 Scopus citations

Abstract

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 η³, 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 η²-HC(PPh₂NPh)₂ structure with coordinated L; this is tested experimentally. The greater tendency for this ligand to be coordinated η³ vs analogous diketiminates is discussed. The nucleophilicity of C_γ 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.

Original language	English
Pages (from-to)	2312-2313
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	126
Issue number	8
DOIs	https://doi.org/10.1021/ja039711y
State	Published - Mar 3 2004

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title = "Multifunctional Behavior by a Bis-(phosphinimino)methanide Ligand: η2-vs η3-coordination vs Bronsted Basicity",

abstract = "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 η3, 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 Br{\o}nsted 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 η2-HC(PPh2NPh)2 structure with coordinated L; this is tested experimentally. The greater tendency for this ligand to be coordinated η3 vs analogous diketiminates is discussed. The nucleophilicity of Cγ 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.",

author = "Christine Bibal and Maren Pink and Smurnyy, \{Yegor D.\} and John Tomaszewski and Caulton, \{Kenneth G.\}",

year = "2004",

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doi = "10.1021/ja039711y",

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T1 - Multifunctional Behavior by a Bis-(phosphinimino)methanide Ligand

T2 - η2-vs η3-coordination vs Bronsted Basicity

AU - Bibal, Christine

AU - Pink, Maren

AU - Smurnyy, Yegor D.

AU - Tomaszewski, John

AU - Caulton, Kenneth G.

PY - 2004/3/3

Y1 - 2004/3/3

N2 - 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 η3, 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 η2-HC(PPh2NPh)2 structure with coordinated L; this is tested experimentally. The greater tendency for this ligand to be coordinated η3 vs analogous diketiminates is discussed. The nucleophilicity of Cγ 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.

AB - 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 η3, 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 η2-HC(PPh2NPh)2 structure with coordinated L; this is tested experimentally. The greater tendency for this ligand to be coordinated η3 vs analogous diketiminates is discussed. The nucleophilicity of Cγ 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.

UR - https://www.scopus.com/pages/publications/1542315167

U2 - 10.1021/ja039711y

DO - 10.1021/ja039711y

M3 - Article

SN - 0002-7863

VL - 126

SP - 2312

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 8

ER -

Multifunctional Behavior by a Bis-(phosphinimino)methanide Ligand: η²-vs η³-coordination vs Bronsted Basicity

Abstract

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