(dme)MCl3(NNPh2) (dme = dimethoxyethane; M = Nb, Ta): A versatile synthon for [Ta - NNPh2] hydrazido(2-) complexes

Ian A. Tonks; John E. Bercaw

doi:10.1021/ic1004193

(dme)MCl₃(NNPh₂) (dme = dimethoxyethane; M = Nb, Ta): A versatile synthon for [Ta - NNPh₂] hydrazido(2-) complexes

Ian A. Tonks, John E. Bercaw

Chemistry (Twin Cities)

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

19 Scopus citations

Abstract

Complexes (dme)TaCl₃(NNPh₂) (1) and (dme)NbCl ₃(NNPh₂) (2) (dme =1,2-dimethoxyethane) were synthesized from MCl₅ and diphenylhydrazine via a Lewis-acid assisted dehydrohalogenation reaction. Monomeric 1 has been characterized by X-ray, IR, UV-vis, ¹H NMR, and ¹³C NMR spectroscopy and contains a κ¹-bound hydrazido(2-) moiety. Unlike the corresponding imido derivatives, 1 is dark blue because of an LMCT that has been lowered in energy as a result of an N_α-N_β antibonding interaction that raises the highest occupied molecular orbital (HOMO). Reaction of 1 with a variety of neutral, mono- and dianionic ligands generates the corresponding ligated complexes retaining the κ¹-bound [Ta-NNPh₂] moiety.

Original language	English (US)
Pages (from-to)	4648-4656
Number of pages	9
Journal	Inorganic chemistry
Volume	49
Issue number	10
DOIs	https://doi.org/10.1021/ic1004193
State	Published - May 17 2010

Publisher link

10.1021/ic1004193

Find It

Find It at U of M Libraries

Cite this

@article{1dab5502ab734a2492d22b7644213b35,

title = "(dme)MCl3(NNPh2) (dme = dimethoxyethane; M = Nb, Ta): A versatile synthon for [Ta - NNPh2] hydrazido(2-) complexes",

abstract = "Complexes (dme)TaCl3(NNPh2) (1) and (dme)NbCl 3(NNPh2) (2) (dme =1,2-dimethoxyethane) were synthesized from MCl5 and diphenylhydrazine via a Lewis-acid assisted dehydrohalogenation reaction. Monomeric 1 has been characterized by X-ray, IR, UV-vis, 1H NMR, and 13C NMR spectroscopy and contains a κ1-bound hydrazido(2-) moiety. Unlike the corresponding imido derivatives, 1 is dark blue because of an LMCT that has been lowered in energy as a result of an Nα-Nβ antibonding interaction that raises the highest occupied molecular orbital (HOMO). Reaction of 1 with a variety of neutral, mono- and dianionic ligands generates the corresponding ligated complexes retaining the κ1-bound [Ta-NNPh2] moiety.",

author = "Tonks, {Ian A.} and Bercaw, {John E.}",

year = "2010",

month = may,

day = "17",

doi = "10.1021/ic1004193",

language = "English (US)",

volume = "49",

pages = "4648--4656",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "10",

}

TY - JOUR

T1 - (dme)MCl3(NNPh2) (dme = dimethoxyethane; M = Nb, Ta)

T2 - A versatile synthon for [Ta - NNPh2] hydrazido(2-) complexes

AU - Tonks, Ian A.

AU - Bercaw, John E.

PY - 2010/5/17

Y1 - 2010/5/17

N2 - Complexes (dme)TaCl3(NNPh2) (1) and (dme)NbCl 3(NNPh2) (2) (dme =1,2-dimethoxyethane) were synthesized from MCl5 and diphenylhydrazine via a Lewis-acid assisted dehydrohalogenation reaction. Monomeric 1 has been characterized by X-ray, IR, UV-vis, 1H NMR, and 13C NMR spectroscopy and contains a κ1-bound hydrazido(2-) moiety. Unlike the corresponding imido derivatives, 1 is dark blue because of an LMCT that has been lowered in energy as a result of an Nα-Nβ antibonding interaction that raises the highest occupied molecular orbital (HOMO). Reaction of 1 with a variety of neutral, mono- and dianionic ligands generates the corresponding ligated complexes retaining the κ1-bound [Ta-NNPh2] moiety.

AB - Complexes (dme)TaCl3(NNPh2) (1) and (dme)NbCl 3(NNPh2) (2) (dme =1,2-dimethoxyethane) were synthesized from MCl5 and diphenylhydrazine via a Lewis-acid assisted dehydrohalogenation reaction. Monomeric 1 has been characterized by X-ray, IR, UV-vis, 1H NMR, and 13C NMR spectroscopy and contains a κ1-bound hydrazido(2-) moiety. Unlike the corresponding imido derivatives, 1 is dark blue because of an LMCT that has been lowered in energy as a result of an Nα-Nβ antibonding interaction that raises the highest occupied molecular orbital (HOMO). Reaction of 1 with a variety of neutral, mono- and dianionic ligands generates the corresponding ligated complexes retaining the κ1-bound [Ta-NNPh2] moiety.

UR - http://www.scopus.com/inward/record.url?scp=77952147339&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=77952147339&partnerID=8YFLogxK

U2 - 10.1021/ic1004193

DO - 10.1021/ic1004193

M3 - Article

C2 - 20402474

AN - SCOPUS:77952147339

SN - 0020-1669

VL - 49

SP - 4648

EP - 4656

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 10

ER -

(dme)MCl₃(NNPh₂) (dme = dimethoxyethane; M = Nb, Ta): A versatile synthon for [Ta - NNPh₂] hydrazido(2-) complexes

Abstract

Publisher link

Find It

Other files and links

Fingerprint

Cite this