Ni(ii) complexes of the phosphine-oxime Ph2PC6H4-2-CH=NOH

Debashis Basu; Toby J. Woods; Thomas B. Rauchfuss

doi:10.1039/c8dt01551a

Ni(ii) complexes of the phosphine-oxime Ph₂PC₆H₄-2-CH=NOH

Debashis Basu, Toby J. Woods, Thomas B. Rauchfuss

Chemistry

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Abstract

We report the solution and structural chemistry of nickel(ii) complexes of the phosphine-oxime Ph₂PC₆H₄-2-CHNOH (PCHNOH). PCHNOH invariably binds in a bidentate manner as illustrated by cis-Ni(PCHNOH)₂Cl₂ and cis-[Ni(PCHNOH)₂]²⁺ (as its BF₄^- salt). Treatment of PCHNOH with Ni(OAc)₂(H₂O)₄ gave charge-neutral trans-[Ni(PCHNO)₂]⁰. Treatment of trans-[Ni(PCHNO)₂]⁰ with BF₃ gave [Ni(PCHNO)₂BF₂]BF₄. The cation features a planar NiP₂N₂ center wherein the pair of oximate groups are linked by the difluoroboryl center. The 1:1 complexes of the oxime and the oximate are illustrated by [Ni(PCHNOH)Cl₂]₂ and [Ni(C₆F₅)(PCHNO)]₂, which feature five- and four-coordinate Ni(ii) centers, respectively. All complexes in this series hydrolyze to give the trinickel oxo-phosphine-oximate complex [Ni₃(PCHNO)₃O]⁺. One feature of the PCHNOH ligand is its wide bite angle combined with its protic OH center. These aspects are manifested in the structures of Ni(PCHNOH)₂Cl₂ and [Ni(PCHNOH)Cl₂]₂, which show intramolecular hydrogen bonding to terminal chloride ligands.

Original language	English (US)
Pages (from-to)	7256-7262
Number of pages	7
Journal	Dalton Transactions
Volume	47
Issue number	21
DOIs	https://doi.org/10.1039/c8dt01551a
State	Published - 2018

ASJC Scopus subject areas

Inorganic Chemistry

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10.1039/c8dt01551a

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@article{3ef0b41300fc4e44b5104816a84e9955,

title = "Ni(ii) complexes of the phosphine-oxime Ph2PC6H4-2-CH=NOH",

abstract = "We report the solution and structural chemistry of nickel(ii) complexes of the phosphine-oxime Ph2PC6H4-2-CHNOH (PCHNOH). PCHNOH invariably binds in a bidentate manner as illustrated by cis-Ni(PCHNOH)2Cl2 and cis-[Ni(PCHNOH)2]2+ (as its BF4- salt). Treatment of PCHNOH with Ni(OAc)2(H2O)4 gave charge-neutral trans-[Ni(PCHNO)2]0. Treatment of trans-[Ni(PCHNO)2]0 with BF3 gave [Ni(PCHNO)2BF2]BF4. The cation features a planar NiP2N2 center wherein the pair of oximate groups are linked by the difluoroboryl center. The 1:1 complexes of the oxime and the oximate are illustrated by [Ni(PCHNOH)Cl2]2 and [Ni(C6F5)(PCHNO)]2, which feature five- and four-coordinate Ni(ii) centers, respectively. All complexes in this series hydrolyze to give the trinickel oxo-phosphine-oximate complex [Ni3(PCHNO)3O]+. One feature of the PCHNOH ligand is its wide bite angle combined with its protic OH center. These aspects are manifested in the structures of Ni(PCHNOH)2Cl2 and [Ni(PCHNOH)Cl2]2, which show intramolecular hydrogen bonding to terminal chloride ligands.",

author = "Debashis Basu and Woods, {Toby J.} and Rauchfuss, {Thomas B.}",

note = "Publisher Copyright: {\textcopyright} 2018 The Royal Society of Chemistry.",

year = "2018",

doi = "10.1039/c8dt01551a",

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volume = "47",

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T1 - Ni(ii) complexes of the phosphine-oxime Ph2PC6H4-2-CH=NOH

AU - Basu, Debashis

AU - Woods, Toby J.

AU - Rauchfuss, Thomas B.

PY - 2018

Y1 - 2018

N2 - We report the solution and structural chemistry of nickel(ii) complexes of the phosphine-oxime Ph2PC6H4-2-CHNOH (PCHNOH). PCHNOH invariably binds in a bidentate manner as illustrated by cis-Ni(PCHNOH)2Cl2 and cis-[Ni(PCHNOH)2]2+ (as its BF4- salt). Treatment of PCHNOH with Ni(OAc)2(H2O)4 gave charge-neutral trans-[Ni(PCHNO)2]0. Treatment of trans-[Ni(PCHNO)2]0 with BF3 gave [Ni(PCHNO)2BF2]BF4. The cation features a planar NiP2N2 center wherein the pair of oximate groups are linked by the difluoroboryl center. The 1:1 complexes of the oxime and the oximate are illustrated by [Ni(PCHNOH)Cl2]2 and [Ni(C6F5)(PCHNO)]2, which feature five- and four-coordinate Ni(ii) centers, respectively. All complexes in this series hydrolyze to give the trinickel oxo-phosphine-oximate complex [Ni3(PCHNO)3O]+. One feature of the PCHNOH ligand is its wide bite angle combined with its protic OH center. These aspects are manifested in the structures of Ni(PCHNOH)2Cl2 and [Ni(PCHNOH)Cl2]2, which show intramolecular hydrogen bonding to terminal chloride ligands.

AB - We report the solution and structural chemistry of nickel(ii) complexes of the phosphine-oxime Ph2PC6H4-2-CHNOH (PCHNOH). PCHNOH invariably binds in a bidentate manner as illustrated by cis-Ni(PCHNOH)2Cl2 and cis-[Ni(PCHNOH)2]2+ (as its BF4- salt). Treatment of PCHNOH with Ni(OAc)2(H2O)4 gave charge-neutral trans-[Ni(PCHNO)2]0. Treatment of trans-[Ni(PCHNO)2]0 with BF3 gave [Ni(PCHNO)2BF2]BF4. The cation features a planar NiP2N2 center wherein the pair of oximate groups are linked by the difluoroboryl center. The 1:1 complexes of the oxime and the oximate are illustrated by [Ni(PCHNOH)Cl2]2 and [Ni(C6F5)(PCHNO)]2, which feature five- and four-coordinate Ni(ii) centers, respectively. All complexes in this series hydrolyze to give the trinickel oxo-phosphine-oximate complex [Ni3(PCHNO)3O]+. One feature of the PCHNOH ligand is its wide bite angle combined with its protic OH center. These aspects are manifested in the structures of Ni(PCHNOH)2Cl2 and [Ni(PCHNOH)Cl2]2, which show intramolecular hydrogen bonding to terminal chloride ligands.

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