Oxidation of Ni3(dpa)4Cl2 and Cu3(dpa)4Cl2: Nickel-nickel bonding interaction, but no copper-copper bonds

John F. Berry; F. Albert Cotton; Lee M. Daniels; Carlos A. Murillo; Xiaoping Wang

doi:10.1021/ic0262740

Oxidation of Ni₃(dpa)₄Cl₂ and Cu₃(dpa)₄Cl₂: Nickel-nickel bonding interaction, but no copper-copper bonds

John F. Berry
, F. Albert Cotton
, Lee M. Daniels
, Carlos A. Murillo
, Xiaoping Wang

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

121 Scopus citations

Abstract

Of the known trinuclear dipyridylamido complexes of the first-row transition metals, M₃(dpa)₄Cl₂ (dpa is the anion of di(2-pyridyl)amine, M = Cr, Co, Ni, Cu), the one-electron-oxidation products of only Cr₃(dpa)₄Cl₂ and Co₃(dpa)₄-Cl₂ have been isolated previously. Here we report one-electron-oxidation products of Ni₃(dpa)₄Cl₂ (1) and Cu₃(dpa)₄-Cl₂ (3): Ni₃(dpa)₄(PF₆)₃ (2) and [Cu₃(dpa)₄Cl₂]SbCl₆ (4). While there are no Ni-Ni bonds in 1, the Ni-Ni distances in 2 are 0.15 Å shorter than those in 1, very suggestive of metal-metal bonding interactions. In contrast, the oxidation of 3 to 4 is accompanied by a lengthening of the Cu-Cu distances, as expected for an increase in electrostatic charge between positively charged nonbonded metal ions, which is further evidence against Cu-Cu bonding in either 3 or 4. A qualitative model of the electronic structures of all [M₃(dpa)₄Cl₂]ⁿ⁺ (n = 0, 1) compounds is presented and discussed.

Original language	English
Pages (from-to)	2418-2427
Number of pages	10
Journal	Inorganic Chemistry
Volume	42
Issue number	7
DOIs	https://doi.org/10.1021/ic0262740
State	Published - Apr 7 2003
Externally published	Yes

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@article{505a3c0f782e44a19fccb950ebfaab3e,

title = "Oxidation of Ni3(dpa)4Cl2 and Cu3(dpa)4Cl2: Nickel-nickel bonding interaction, but no copper-copper bonds",

abstract = "Of the known trinuclear dipyridylamido complexes of the first-row transition metals, M3(dpa)4Cl2 (dpa is the anion of di(2-pyridyl)amine, M = Cr, Co, Ni, Cu), the one-electron-oxidation products of only Cr3(dpa)4Cl2 and Co3(dpa)4-Cl2 have been isolated previously. Here we report one-electron-oxidation products of Ni3(dpa)4Cl2 (1) and Cu3(dpa)4-Cl2 (3): Ni3(dpa)4(PF6)3 (2) and [Cu3(dpa)4Cl2]SbCl6 (4). While there are no Ni-Ni bonds in 1, the Ni-Ni distances in 2 are 0.15 {\AA} shorter than those in 1, very suggestive of metal-metal bonding interactions. In contrast, the oxidation of 3 to 4 is accompanied by a lengthening of the Cu-Cu distances, as expected for an increase in electrostatic charge between positively charged nonbonded metal ions, which is further evidence against Cu-Cu bonding in either 3 or 4. A qualitative model of the electronic structures of all [M3(dpa)4Cl2]n+ (n = 0, 1) compounds is presented and discussed.",

author = "Berry, \{John F.\} and Cotton, \{F. Albert\} and Daniels, \{Lee M.\} and Murillo, \{Carlos A.\} and Xiaoping Wang",

year = "2003",

month = apr,

day = "7",

doi = "10.1021/ic0262740",

language = "English",

volume = "42",

pages = "2418--2427",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "7",

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TY - JOUR

T1 - Oxidation of Ni3(dpa)4Cl2 and Cu3(dpa)4Cl2

T2 - Nickel-nickel bonding interaction, but no copper-copper bonds

AU - Berry, John F.

AU - Cotton, F. Albert

AU - Daniels, Lee M.

AU - Murillo, Carlos A.

AU - Wang, Xiaoping

PY - 2003/4/7

Y1 - 2003/4/7

N2 - Of the known trinuclear dipyridylamido complexes of the first-row transition metals, M3(dpa)4Cl2 (dpa is the anion of di(2-pyridyl)amine, M = Cr, Co, Ni, Cu), the one-electron-oxidation products of only Cr3(dpa)4Cl2 and Co3(dpa)4-Cl2 have been isolated previously. Here we report one-electron-oxidation products of Ni3(dpa)4Cl2 (1) and Cu3(dpa)4-Cl2 (3): Ni3(dpa)4(PF6)3 (2) and [Cu3(dpa)4Cl2]SbCl6 (4). While there are no Ni-Ni bonds in 1, the Ni-Ni distances in 2 are 0.15 Å shorter than those in 1, very suggestive of metal-metal bonding interactions. In contrast, the oxidation of 3 to 4 is accompanied by a lengthening of the Cu-Cu distances, as expected for an increase in electrostatic charge between positively charged nonbonded metal ions, which is further evidence against Cu-Cu bonding in either 3 or 4. A qualitative model of the electronic structures of all [M3(dpa)4Cl2]n+ (n = 0, 1) compounds is presented and discussed.

AB - Of the known trinuclear dipyridylamido complexes of the first-row transition metals, M3(dpa)4Cl2 (dpa is the anion of di(2-pyridyl)amine, M = Cr, Co, Ni, Cu), the one-electron-oxidation products of only Cr3(dpa)4Cl2 and Co3(dpa)4-Cl2 have been isolated previously. Here we report one-electron-oxidation products of Ni3(dpa)4Cl2 (1) and Cu3(dpa)4-Cl2 (3): Ni3(dpa)4(PF6)3 (2) and [Cu3(dpa)4Cl2]SbCl6 (4). While there are no Ni-Ni bonds in 1, the Ni-Ni distances in 2 are 0.15 Å shorter than those in 1, very suggestive of metal-metal bonding interactions. In contrast, the oxidation of 3 to 4 is accompanied by a lengthening of the Cu-Cu distances, as expected for an increase in electrostatic charge between positively charged nonbonded metal ions, which is further evidence against Cu-Cu bonding in either 3 or 4. A qualitative model of the electronic structures of all [M3(dpa)4Cl2]n+ (n = 0, 1) compounds is presented and discussed.

UR - https://www.scopus.com/pages/publications/0037425167

U2 - 10.1021/ic0262740

DO - 10.1021/ic0262740

M3 - Article

AN - SCOPUS:0037425167

SN - 0020-1669

VL - 42

SP - 2418

EP - 2427

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

ER -

Oxidation of Ni₃(dpa)₄Cl₂ and Cu₃(dpa)₄Cl₂: Nickel-nickel bonding interaction, but no copper-copper bonds

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