Organo-tricyanoborates as tectons: Illustrative coordination polymers based on copper(I) derivatives

Haijun Yao; Matthew L. Kuhlman; Thomas B. Rauchfuss; Scott R. Wilson

doi:10.1021/ic0506153

Organo-tricyanoborates as tectons: Illustrative coordination polymers based on copper(I) derivatives

Haijun Yao, Matthew L. Kuhlman, Thomas B. Rauchfuss, Scott R. Wilson

Chemistry

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Abstract

The first systematic study on the use of tricyanoborates as ligands is presented. The tricyanoborates [RB(CN)₃]^- (R = oct and Ph) can be prepared by direct cyanation of RBCl₂ precursors as well as by thermolysis of the corresponding isocyanides [RB(NC)₃] ^-. The first organo-cyanogallates [RGa(CN)₃]^- (R = Bu, C₆H₂-2,4,6-Me₃) were prepared from the corresponding dichloride, the structure of Et₄N[mesGa(CN) ₃] being confirmed crystallographically. The reaction of equimolar [RB(CN)₃]^- (R = oct, Ph) and [Cu(MeCN)₄] ⁺ afforded two-dimensional polymers [RB-(CN)₃Cu(NCMe)]. The sheets arise via conjoined hexagonal B₃Cu₃(CN) ₆ rings with chair conformations. The reaction of excess [PhB(CN)₃]^- and [Cu(MeCN)₄]⁺ gives the polymer [K(18-crown-6)]{Cu[PhB(CN)₃]₂}. Treatment of [PhB(CN)₃]^- with [Cu(PCy₃)₂(NCMe) _x]PF₆ gave the one-dimensional polymer [PhB(CN) ₃Cu(PCy₃)₂], wherein two of the three BCN substituents are coordinated.

Original language	English (US)
Pages (from-to)	6256-6264
Number of pages	9
Journal	Inorganic Chemistry
Volume	44
Issue number	18
DOIs	https://doi.org/10.1021/ic0506153
State	Published - Sep 5 2005

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Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic0506153

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title = "Organo-tricyanoborates as tectons: Illustrative coordination polymers based on copper(I) derivatives",

abstract = "The first systematic study on the use of tricyanoborates as ligands is presented. The tricyanoborates [RB(CN)3]- (R = oct and Ph) can be prepared by direct cyanation of RBCl2 precursors as well as by thermolysis of the corresponding isocyanides [RB(NC)3] -. The first organo-cyanogallates [RGa(CN)3]- (R = Bu, C6H2-2,4,6-Me3) were prepared from the corresponding dichloride, the structure of Et4N[mesGa(CN) 3] being confirmed crystallographically. The reaction of equimolar [RB(CN)3]- (R = oct, Ph) and [Cu(MeCN)4] + afforded two-dimensional polymers [RB-(CN)3Cu(NCMe)]. The sheets arise via conjoined hexagonal B3Cu3(CN) 6 rings with chair conformations. The reaction of excess [PhB(CN)3]- and [Cu(MeCN)4]+ gives the polymer [K(18-crown-6)]{Cu[PhB(CN)3]2}. Treatment of [PhB(CN)3]- with [Cu(PCy3)2(NCMe) x]PF6 gave the one-dimensional polymer [PhB(CN) 3Cu(PCy3)2], wherein two of the three BCN substituents are coordinated.",

author = "Haijun Yao and Kuhlman, {Matthew L.} and Rauchfuss, {Thomas B.} and Wilson, {Scott R.}",

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AU - Wilson, Scott R.

PY - 2005/9/5

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N2 - The first systematic study on the use of tricyanoborates as ligands is presented. The tricyanoborates [RB(CN)3]- (R = oct and Ph) can be prepared by direct cyanation of RBCl2 precursors as well as by thermolysis of the corresponding isocyanides [RB(NC)3] -. The first organo-cyanogallates [RGa(CN)3]- (R = Bu, C6H2-2,4,6-Me3) were prepared from the corresponding dichloride, the structure of Et4N[mesGa(CN) 3] being confirmed crystallographically. The reaction of equimolar [RB(CN)3]- (R = oct, Ph) and [Cu(MeCN)4] + afforded two-dimensional polymers [RB-(CN)3Cu(NCMe)]. The sheets arise via conjoined hexagonal B3Cu3(CN) 6 rings with chair conformations. The reaction of excess [PhB(CN)3]- and [Cu(MeCN)4]+ gives the polymer [K(18-crown-6)]{Cu[PhB(CN)3]2}. Treatment of [PhB(CN)3]- with [Cu(PCy3)2(NCMe) x]PF6 gave the one-dimensional polymer [PhB(CN) 3Cu(PCy3)2], wherein two of the three BCN substituents are coordinated.

AB - The first systematic study on the use of tricyanoborates as ligands is presented. The tricyanoborates [RB(CN)3]- (R = oct and Ph) can be prepared by direct cyanation of RBCl2 precursors as well as by thermolysis of the corresponding isocyanides [RB(NC)3] -. The first organo-cyanogallates [RGa(CN)3]- (R = Bu, C6H2-2,4,6-Me3) were prepared from the corresponding dichloride, the structure of Et4N[mesGa(CN) 3] being confirmed crystallographically. The reaction of equimolar [RB(CN)3]- (R = oct, Ph) and [Cu(MeCN)4] + afforded two-dimensional polymers [RB-(CN)3Cu(NCMe)]. The sheets arise via conjoined hexagonal B3Cu3(CN) 6 rings with chair conformations. The reaction of excess [PhB(CN)3]- and [Cu(MeCN)4]+ gives the polymer [K(18-crown-6)]{Cu[PhB(CN)3]2}. Treatment of [PhB(CN)3]- with [Cu(PCy3)2(NCMe) x]PF6 gave the one-dimensional polymer [PhB(CN) 3Cu(PCy3)2], wherein two of the three BCN substituents are coordinated.

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Organo-tricyanoborates as tectons: Illustrative coordination polymers based on copper(I) derivatives

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