Redox-Initiated Reactivity of Dinuclear β-Diketiminatoniobium Imido Complexes

Benjamin M. Kriegel; Lara C.E. Naested; Grégory Nocton; K. V. Lakshmi; Trevor D. Lohrey; Robert G. Bergman; John Arnold

doi:10.1021/acs.inorgchem.6b02735

Redox-Initiated Reactivity of Dinuclear β-Diketiminatoniobium Imido Complexes

Benjamin M. Kriegel
, Lara C.E. Naested
, Grégory Nocton
, K. V. Lakshmi
, Trevor D. Lohrey
, Robert G. Bergman
, John Arnold

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

Abstract

High-valent dichloride and dimethylniobium complexes 1 and 2 bearing tert-butylimido and N,N′-bis(2,4,6-trimethylphenyl)-β-diketiminate (BDI^Ar) ligands were prepared. The dimethyl complex reacted with dihydrogen to release methane and generate the hydride-bridged diniobium(IV) complex 3 in high yield. One-electron oxidation of 3 with silver salts resulted in the release of dihydrogen and conversion to a mixed-valent Nb^III-Nb^IV complex, 4, that displayed a frozen-solution X-band electron paramagnetic resonance signal consistent with a slight dissymmetry between the two Nb centers. Spectroscopic and computational analysis supported the presence of Nb-Nb σ-bonding interactions in both 3 and 4. Finally, one-electron reduction of 4 resulted in conversion to the highly dissymmetric Nb^V-Nb^V dimer 5 that formed from the reductive C-N bond cleavage of one of the BDI^Ar supporting ligands.

Original language	English
Pages (from-to)	1626-1637
Number of pages	12
Journal	Inorganic Chemistry
Volume	56
Issue number	3
DOIs	https://doi.org/10.1021/acs.inorgchem.6b02735
Publication status	Published - 6 Feb 2017
Externally published	Yes

Access to Document

10.1021/acs.inorgchem.6b02735

Cite this

@article{95a27d1f55404254b5bc7fc633fd5409,

title = "Redox-Initiated Reactivity of Dinuclear β-Diketiminatoniobium Imido Complexes",

abstract = "High-valent dichloride and dimethylniobium complexes 1 and 2 bearing tert-butylimido and N,N′-bis(2,4,6-trimethylphenyl)-β-diketiminate (BDIAr) ligands were prepared. The dimethyl complex reacted with dihydrogen to release methane and generate the hydride-bridged diniobium(IV) complex 3 in high yield. One-electron oxidation of 3 with silver salts resulted in the release of dihydrogen and conversion to a mixed-valent NbIII-NbIV complex, 4, that displayed a frozen-solution X-band electron paramagnetic resonance signal consistent with a slight dissymmetry between the two Nb centers. Spectroscopic and computational analysis supported the presence of Nb-Nb σ-bonding interactions in both 3 and 4. Finally, one-electron reduction of 4 resulted in conversion to the highly dissymmetric NbV-NbV dimer 5 that formed from the reductive C-N bond cleavage of one of the BDIAr supporting ligands.",

author = "Kriegel, \{Benjamin M.\} and Naested, \{Lara C.E.\} and Gr{\'e}gory Nocton and Lakshmi, \{K. V.\} and Lohrey, \{Trevor D.\} and Bergman, \{Robert G.\} and John Arnold",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = feb,

day = "6",

doi = "10.1021/acs.inorgchem.6b02735",

language = "English",

volume = "56",

pages = "1626--1637",

journal = "Inorganic Chemistry",

issn = "0020-1669",

number = "3",

}

TY - JOUR

T1 - Redox-Initiated Reactivity of Dinuclear β-Diketiminatoniobium Imido Complexes

AU - Kriegel, Benjamin M.

AU - Naested, Lara C.E.

AU - Nocton, Grégory

AU - Lakshmi, K. V.

AU - Lohrey, Trevor D.

AU - Bergman, Robert G.

AU - Arnold, John

PY - 2017/2/6

Y1 - 2017/2/6

N2 - High-valent dichloride and dimethylniobium complexes 1 and 2 bearing tert-butylimido and N,N′-bis(2,4,6-trimethylphenyl)-β-diketiminate (BDIAr) ligands were prepared. The dimethyl complex reacted with dihydrogen to release methane and generate the hydride-bridged diniobium(IV) complex 3 in high yield. One-electron oxidation of 3 with silver salts resulted in the release of dihydrogen and conversion to a mixed-valent NbIII-NbIV complex, 4, that displayed a frozen-solution X-band electron paramagnetic resonance signal consistent with a slight dissymmetry between the two Nb centers. Spectroscopic and computational analysis supported the presence of Nb-Nb σ-bonding interactions in both 3 and 4. Finally, one-electron reduction of 4 resulted in conversion to the highly dissymmetric NbV-NbV dimer 5 that formed from the reductive C-N bond cleavage of one of the BDIAr supporting ligands.

AB - High-valent dichloride and dimethylniobium complexes 1 and 2 bearing tert-butylimido and N,N′-bis(2,4,6-trimethylphenyl)-β-diketiminate (BDIAr) ligands were prepared. The dimethyl complex reacted with dihydrogen to release methane and generate the hydride-bridged diniobium(IV) complex 3 in high yield. One-electron oxidation of 3 with silver salts resulted in the release of dihydrogen and conversion to a mixed-valent NbIII-NbIV complex, 4, that displayed a frozen-solution X-band electron paramagnetic resonance signal consistent with a slight dissymmetry between the two Nb centers. Spectroscopic and computational analysis supported the presence of Nb-Nb σ-bonding interactions in both 3 and 4. Finally, one-electron reduction of 4 resulted in conversion to the highly dissymmetric NbV-NbV dimer 5 that formed from the reductive C-N bond cleavage of one of the BDIAr supporting ligands.

U2 - 10.1021/acs.inorgchem.6b02735

DO - 10.1021/acs.inorgchem.6b02735

M3 - Article

C2 - 28098983

AN - SCOPUS:85011866724

SN - 0020-1669

VL - 56

SP - 1626

EP - 1637

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3

ER -

Redox-Initiated Reactivity of Dinuclear β-Diketiminatoniobium Imido Complexes

Abstract

Access to Document

Fingerprint

Cite this