Synthesis and Redox Chemistry of a Tantalum Alkylidene Complex Bearing a Metallaimidazole Ring

Benjamin M.  Kriegel; Nikolas Kaltsoyannis; Ruchira Chatterjee; Robert G Bergman; John Arnold

doi:10.1021/acs.organomet.7b00448

Synthesis and Redox Chemistry of a Tantalum Alkylidene Complex Bearing a Metallaimidazole Ring

Benjamin M. Kriegel, Nikolas Kaltsoyannis, Ruchira Chatterjee, Robert G Bergman, John Arnold

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Abstract

The cyclometalated tantalum(V) terminal hydride complex {ArNC(Me)CHC(Me)N[2-(CHMeCH2)-6-iPr-C6H3]}(η2-N(Xyl)CH)Ta(NtBu) reacts cleanly with 2 equiv of 2,6-dimethylphenyl isocyanide via migratory insertion to give a product containing a unique metallaimidazole ring. This complex can be reversibly oxidized by one electron, either electrochemically or chemically, to give a tantalum radical cation species. DFT calculations, as well as X-ray crystallographic and EPR spectroscopic data, are consistent with the electron being removed from an orbital primarily composed of Ta–C π-bonding character but also delocalized over the tantalaimidazole ring.

Original language	English
Pages (from-to)	3520–3529
Journal	Organometallics
Volume	36
Early online date	21 Aug 2017
DOIs	https://doi.org/10.1021/acs.organomet.7b00448
Publication status	Published - 2017

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tantalaimidazole paper_AAMAccepted author manuscript, 7.81 MB

CCDC 1555443: Experimental Crystal Structure Determination
Kriegel, B. M. (Contributor), Kaltsoyannis, N. (Contributor), Chatterjee, R. (Contributor), Bergman, R. G. (Contributor) & Arnold, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1p6kl1, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p6kl1&sid=DataCite
Dataset
CCDC 1555444: Experimental Crystal Structure Determination
Kriegel, B. M. (Contributor), Kaltsoyannis, N. (Contributor), Chatterjee, R. (Contributor), Bergman, R. G. (Contributor) & Arnold, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1p6km2, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p6km2&sid=DataCite
Dataset
CCDC 1555445: Experimental Crystal Structure Determination
Kriegel, B. M. (Contributor), Kaltsoyannis, N. (Contributor), Chatterjee, R. (Contributor), Bergman, R. G. (Contributor) & Arnold, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1p6kn3, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p6kn3&sid=DataCite
Dataset

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title = "Synthesis and Redox Chemistry of a Tantalum Alkylidene Complex Bearing a Metallaimidazole Ring",

abstract = "The cyclometalated tantalum(V) terminal hydride complex {ArNC(Me)CHC(Me)N[2-(CHMeCH2)-6-iPr-C6H3]}(η2-N(Xyl)CH)Ta(NtBu) reacts cleanly with 2 equiv of 2,6-dimethylphenyl isocyanide via migratory insertion to give a product containing a unique metallaimidazole ring. This complex can be reversibly oxidized by one electron, either electrochemically or chemically, to give a tantalum radical cation species. DFT calculations, as well as X-ray crystallographic and EPR spectroscopic data, are consistent with the electron being removed from an orbital primarily composed of Ta–C π-bonding character but also delocalized over the tantalaimidazole ring.",

author = "Kriegel, {Benjamin M.} and Nikolas Kaltsoyannis and Ruchira Chatterjee and Bergman, {Robert G} and John Arnold",

year = "2017",

doi = "10.1021/acs.organomet.7b00448",

language = "English",

volume = "36",

pages = "3520–3529",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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T1 - Synthesis and Redox Chemistry of a Tantalum Alkylidene Complex Bearing a Metallaimidazole Ring

AU - Kriegel, Benjamin M.

AU - Kaltsoyannis, Nikolas

AU - Chatterjee, Ruchira

AU - Bergman, Robert G

AU - Arnold, John

PY - 2017

Y1 - 2017

N2 - The cyclometalated tantalum(V) terminal hydride complex {ArNC(Me)CHC(Me)N[2-(CHMeCH2)-6-iPr-C6H3]}(η2-N(Xyl)CH)Ta(NtBu) reacts cleanly with 2 equiv of 2,6-dimethylphenyl isocyanide via migratory insertion to give a product containing a unique metallaimidazole ring. This complex can be reversibly oxidized by one electron, either electrochemically or chemically, to give a tantalum radical cation species. DFT calculations, as well as X-ray crystallographic and EPR spectroscopic data, are consistent with the electron being removed from an orbital primarily composed of Ta–C π-bonding character but also delocalized over the tantalaimidazole ring.

AB - The cyclometalated tantalum(V) terminal hydride complex {ArNC(Me)CHC(Me)N[2-(CHMeCH2)-6-iPr-C6H3]}(η2-N(Xyl)CH)Ta(NtBu) reacts cleanly with 2 equiv of 2,6-dimethylphenyl isocyanide via migratory insertion to give a product containing a unique metallaimidazole ring. This complex can be reversibly oxidized by one electron, either electrochemically or chemically, to give a tantalum radical cation species. DFT calculations, as well as X-ray crystallographic and EPR spectroscopic data, are consistent with the electron being removed from an orbital primarily composed of Ta–C π-bonding character but also delocalized over the tantalaimidazole ring.

U2 - 10.1021/acs.organomet.7b00448

DO - 10.1021/acs.organomet.7b00448

M3 - Article

SN - 0276-7333

VL - 36

SP - 3520

EP - 3529

JO - Organometallics

JF - Organometallics

ER -

Synthesis and Redox Chemistry of a Tantalum Alkylidene Complex Bearing a Metallaimidazole Ring

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CCDC 1555443: Experimental Crystal Structure Determination

CCDC 1555444: Experimental Crystal Structure Determination

CCDC 1555445: Experimental Crystal Structure Determination

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