Tin-capped trinuclear nickel clusters: Redox isomerism between μ3-stannyl and μ3-stannylene clusters of the class [Ni3(dppm)3(μ3-l)(μ3 -SnClx)]n+ (x = 2, n = 1; x = 3, n = 0)

Brian K. Breedlove; Philip E. Fanwick; Clifford P. Kubiak

doi:10.1021/ic020108a

Tin-capped trinuclear nickel clusters: Redox isomerism between μ₃-stannyl and μ₃-stannylene clusters of the class [Ni₃(dppm)₃(μ₃-l)(μ₃ -SnCl_x)]ⁿ⁺ (x = 2, n = 1; x = 3, n = 0)

Brian K. Breedlove, Philip E. Fanwick, Clifford P. Kubiak

SCI - Chemistry

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

14 Citations (Scopus)

Abstract

The reaction of Ni₃(dppm)₃(μ₃-l)₂ with sodium trichlorostannate affords the first tin-capped nickel cluster Ni₃(dppm)₃(μ₃-l)(μ₃ -SnCl₃) (1). A site of coordinative unsaturation at tin can be introduced by the reaction of 1 with Tl[PF₆] yielding the stannylene-capped cluster [Ni₃(dppm)₃(μ₃-l)(μ₃ -SnCl2)]⁺ (2). Clusters 1 and 2 were characterized by ³¹P NMR, X-ray diffraction, and cyclic voltammetry (CV). Clusters 1 and 2 exhibit single electron redox chemistries, [Ni₃-(dppm)₃(μ₃-l)(μ₃ -SnCl₃)]^0/.-, [Ni₃(dppm)₃(μ₃-l)(μ₃ -SnCl₂)]^+/0, that together comprise a redox equilibrium. Thus, electrochemical reduction of 1 produces first the 49e^- cluster radical anion [Ni₃-(dppm)₃(μ₃-l)(μ₃ -SnCl₃)]^.- which then yields the reduced form of 2, [Ni₃(dppm)₃(μ₃-l)(μ₃ -SnCl₂)], upon chloride dissociation.

Original language	English
Pages (from-to)	4306-4308
Number of pages	3
Journal	Inorganic Chemistry
Volume	41
Issue number	17
DOIs	https://doi.org/10.1021/ic020108a
Publication status	Published - 2002 Aug 26

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@article{34351aac82074618a93cfe2f6b183ba4,

title = "Tin-capped trinuclear nickel clusters: Redox isomerism between μ3-stannyl and μ3-stannylene clusters of the class [Ni3(dppm)3(μ3-l)(μ3 -SnClx)]n+ (x = 2, n = 1; x = 3, n = 0)",

abstract = "The reaction of Ni3(dppm)3(μ3-l)2 with sodium trichlorostannate affords the first tin-capped nickel cluster Ni3(dppm)3(μ3-l)(μ3 -SnCl3) (1). A site of coordinative unsaturation at tin can be introduced by the reaction of 1 with Tl[PF6] yielding the stannylene-capped cluster [Ni3(dppm)3(μ3-l)(μ3 -SnCl2)]+ (2). Clusters 1 and 2 were characterized by 31P NMR, X-ray diffraction, and cyclic voltammetry (CV). Clusters 1 and 2 exhibit single electron redox chemistries, [Ni3-(dppm)3(μ3-l)(μ3 -SnCl3)]0/.-, [Ni3(dppm)3(μ3-l)(μ3 -SnCl2)]+/0, that together comprise a redox equilibrium. Thus, electrochemical reduction of 1 produces first the 49e- cluster radical anion [Ni3-(dppm)3(μ3-l)(μ3 -SnCl3)].- which then yields the reduced form of 2, [Ni3(dppm)3(μ3-l)(μ3 -SnCl2)], upon chloride dissociation.",

author = "Breedlove, {Brian K.} and Fanwick, {Philip E.} and Kubiak, {Clifford P.}",

year = "2002",

month = aug,

day = "26",

doi = "10.1021/ic020108a",

language = "English",

volume = "41",

pages = "4306--4308",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "17",

}

Tin-capped trinuclear nickel clusters: Redox isomerism between μ₃-stannyl and μ₃-stannylene clusters of the class [Ni₃(dppm)₃(μ₃-l)(μ₃ -SnCl_x)]ⁿ⁺ (x = 2, n = 1; x = 3, n = 0). / Breedlove, Brian K.; Fanwick, Philip E.; Kubiak, Clifford P.
In: Inorganic Chemistry, Vol. 41, No. 17, 26.08.2002, p. 4306-4308.

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

TY - JOUR

T1 - Tin-capped trinuclear nickel clusters

T2 - Redox isomerism between μ3-stannyl and μ3-stannylene clusters of the class [Ni3(dppm)3(μ3-l)(μ3 -SnClx)]n+ (x = 2, n = 1; x = 3, n = 0)

AU - Breedlove, Brian K.

AU - Fanwick, Philip E.

AU - Kubiak, Clifford P.

PY - 2002/8/26

Y1 - 2002/8/26

N2 - The reaction of Ni3(dppm)3(μ3-l)2 with sodium trichlorostannate affords the first tin-capped nickel cluster Ni3(dppm)3(μ3-l)(μ3 -SnCl3) (1). A site of coordinative unsaturation at tin can be introduced by the reaction of 1 with Tl[PF6] yielding the stannylene-capped cluster [Ni3(dppm)3(μ3-l)(μ3 -SnCl2)]+ (2). Clusters 1 and 2 were characterized by 31P NMR, X-ray diffraction, and cyclic voltammetry (CV). Clusters 1 and 2 exhibit single electron redox chemistries, [Ni3-(dppm)3(μ3-l)(μ3 -SnCl3)]0/.-, [Ni3(dppm)3(μ3-l)(μ3 -SnCl2)]+/0, that together comprise a redox equilibrium. Thus, electrochemical reduction of 1 produces first the 49e- cluster radical anion [Ni3-(dppm)3(μ3-l)(μ3 -SnCl3)].- which then yields the reduced form of 2, [Ni3(dppm)3(μ3-l)(μ3 -SnCl2)], upon chloride dissociation.

AB - The reaction of Ni3(dppm)3(μ3-l)2 with sodium trichlorostannate affords the first tin-capped nickel cluster Ni3(dppm)3(μ3-l)(μ3 -SnCl3) (1). A site of coordinative unsaturation at tin can be introduced by the reaction of 1 with Tl[PF6] yielding the stannylene-capped cluster [Ni3(dppm)3(μ3-l)(μ3 -SnCl2)]+ (2). Clusters 1 and 2 were characterized by 31P NMR, X-ray diffraction, and cyclic voltammetry (CV). Clusters 1 and 2 exhibit single electron redox chemistries, [Ni3-(dppm)3(μ3-l)(μ3 -SnCl3)]0/.-, [Ni3(dppm)3(μ3-l)(μ3 -SnCl2)]+/0, that together comprise a redox equilibrium. Thus, electrochemical reduction of 1 produces first the 49e- cluster radical anion [Ni3-(dppm)3(μ3-l)(μ3 -SnCl3)].- which then yields the reduced form of 2, [Ni3(dppm)3(μ3-l)(μ3 -SnCl2)], upon chloride dissociation.

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U2 - 10.1021/ic020108a

DO - 10.1021/ic020108a

M3 - Article

C2 - 12184742

AN - SCOPUS:0037179114

SN - 0020-1669

VL - 41

SP - 4306

EP - 4308

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 17

ER -

Tin-capped trinuclear nickel clusters: Redox isomerism between μ₃-stannyl and μ₃-stannylene clusters of the class [Ni₃(dppm)₃(μ₃-l)(μ₃ -SnCl_x)]ⁿ⁺ (x = 2, n = 1; x = 3, n = 0)

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