Chloride metathesis and dimethylamide transfer in the reaction of TaCl(NMe2)4 with ZnMe2 and MeMgCl: Spectroscopic studies and X-ray diffraction structures of TaCl(Me)(NMe 2)3 and ZnCl2(NHMe2)2

Xiaoping Wang; Shih Huang Huang; Michael G. Richmond

doi:10.1007/s10870-009-9630-0

Chloride metathesis and dimethylamide transfer in the reaction of TaCl(NMe₂)₄ with ZnMe₂ and MeMgCl: Spectroscopic studies and X-ray diffraction structures of TaCl(Me)(NMe ₂)₃ and ZnCl₂(NHMe₂)₂

Xiaoping Wang, Shih Huang Huang, Michael G. Richmond

Single Crystal Diffraction

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

4 Scopus citations

Abstract

Treatment of TaCl(NMe₂)₄ with ZnMe₂ in pentane furnishes a mixture of TaCl(Me)(NMe₂)₃, TaMe(NMe₂)₄, and Ta(NMe₂)₅ as the principal reaction products based on ¹H NMR spectroscopy. Depending upon the work-up conditions employed, the compounds TaCl(Me)(NMe ₂)₃ and ZnCl₂(NHMe₂)₂ have been isolated and their molecular structures established by X-ray crystallography. TaCl(Me)(NMe₂)₃ crystallizes in the orthorhombic space group Pna2₁, a = 13.644(4) Å, b = 12.934(4) Å, c = 6.992(2) Å, V = 1233.9(7) Å³, Z = 4, and d _calc = 1.958 Mg/m³; R = 0.0316 and wR ₂ = 0.0707 for 2630 reflections with I > 2σ(I). The molecular structure of TaCl(Me)(NMe₂)₃ consists of a trigonal bipyramidal core and contains axial and equatorial chlorine and methyl groups, respectively. ZnCl₂(NHMe₂)₂ crystallizes in the orthorhombic space group P2₁2₁2₁, a = 5.759(1) Å, b = 10.810(2) Å, c = 15.174(3) Å, V = 944.1(3) Å³, Z = 4, d _calc = 1.593 Mg/m³; R = 0.0213 and wR ₂ = 0.0494 for 1872 reflections with I > 2σ(I). ZnCl₂(NHMe ₂)₂ exhibits a tetrahedral motif and represents the first reported four-coordinate zinc(II) compound containing acyclic monodentate secondary amine groups. The reaction between TaCl(NMe₂)₄ and MeMgCl afforded a mixture of tantalum products, of which TaCl(Me)(NMe ₂)₃ and Ta(NMe₂)₅ were found as the major products by ¹H NMR spectroscopy.

Original language	English
Pages (from-to)	173-178
Number of pages	6
Journal	Journal of Chemical Crystallography
Volume	40
Issue number	2
DOIs	https://doi.org/10.1007/s10870-009-9630-0
State	Published - Feb 2010

Funding

Acknowledgments Financial support from the Robert A. Welch Foundation (Grant B-1093-MGR) is greatly appreciated, and X. Wang acknowledges the support by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC05-00OR22725 managed by UT Battelle, LLC.

Funders	Funder number
Robert A. Welch Foundation	B-1093-MGR
U.S. Department of Energy
Office of Science

Keywords

Crystallography
Metal amides
Organometallics
Tantalum compounds
Zinc compounds

Access to Document

10.1007/s10870-009-9630-0

Cite this

@article{11a592f4b37f47919efb11b4d790988b,

title = "Chloride metathesis and dimethylamide transfer in the reaction of TaCl(NMe2)4 with ZnMe2 and MeMgCl: Spectroscopic studies and X-ray diffraction structures of TaCl(Me)(NMe 2)3 and ZnCl2(NHMe2)2",

abstract = "Treatment of TaCl(NMe2)4 with ZnMe2 in pentane furnishes a mixture of TaCl(Me)(NMe2)3, TaMe(NMe2)4, and Ta(NMe2)5 as the principal reaction products based on 1H NMR spectroscopy. Depending upon the work-up conditions employed, the compounds TaCl(Me)(NMe 2)3 and ZnCl2(NHMe2)2 have been isolated and their molecular structures established by X-ray crystallography. TaCl(Me)(NMe2)3 crystallizes in the orthorhombic space group Pna21, a = 13.644(4) {\AA}, b = 12.934(4) {\AA}, c = 6.992(2) {\AA}, V = 1233.9(7) {\AA}3, Z = 4, and d calc = 1.958 Mg/m3; R = 0.0316 and wR 2 = 0.0707 for 2630 reflections with I > 2σ(I). The molecular structure of TaCl(Me)(NMe2)3 consists of a trigonal bipyramidal core and contains axial and equatorial chlorine and methyl groups, respectively. ZnCl2(NHMe2)2 crystallizes in the orthorhombic space group P212121, a = 5.759(1) {\AA}, b = 10.810(2) {\AA}, c = 15.174(3) {\AA}, V = 944.1(3) {\AA}3, Z = 4, d calc = 1.593 Mg/m3; R = 0.0213 and wR 2 = 0.0494 for 1872 reflections with I > 2σ(I). ZnCl2(NHMe 2)2 exhibits a tetrahedral motif and represents the first reported four-coordinate zinc(II) compound containing acyclic monodentate secondary amine groups. The reaction between TaCl(NMe2)4 and MeMgCl afforded a mixture of tantalum products, of which TaCl(Me)(NMe 2)3 and Ta(NMe2)5 were found as the major products by 1H NMR spectroscopy.",

keywords = "Crystallography, Metal amides, Organometallics, Tantalum compounds, Zinc compounds",

author = "Xiaoping Wang and Huang, {Shih Huang} and Richmond, {Michael G.}",

year = "2010",

month = feb,

doi = "10.1007/s10870-009-9630-0",

language = "English",

volume = "40",

pages = "173--178",

journal = "Journal of Chemical Crystallography",

issn = "1074-1542",

publisher = "Springer",

number = "2",

}

Chloride metathesis and dimethylamide transfer in the reaction of TaCl(NMe₂)₄ with ZnMe₂ and MeMgCl: Spectroscopic studies and X-ray diffraction structures of TaCl(Me)(NMe ₂)₃ and ZnCl₂(NHMe₂)₂. / Wang, Xiaoping; Huang, Shih Huang; Richmond, Michael G.
In: Journal of Chemical Crystallography, Vol. 40, No. 2, 02.2010, p. 173-178.

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

TY - JOUR

T1 - Chloride metathesis and dimethylamide transfer in the reaction of TaCl(NMe2)4 with ZnMe2 and MeMgCl

T2 - Spectroscopic studies and X-ray diffraction structures of TaCl(Me)(NMe 2)3 and ZnCl2(NHMe2)2

AU - Wang, Xiaoping

AU - Huang, Shih Huang

AU - Richmond, Michael G.

PY - 2010/2

Y1 - 2010/2

N2 - Treatment of TaCl(NMe2)4 with ZnMe2 in pentane furnishes a mixture of TaCl(Me)(NMe2)3, TaMe(NMe2)4, and Ta(NMe2)5 as the principal reaction products based on 1H NMR spectroscopy. Depending upon the work-up conditions employed, the compounds TaCl(Me)(NMe 2)3 and ZnCl2(NHMe2)2 have been isolated and their molecular structures established by X-ray crystallography. TaCl(Me)(NMe2)3 crystallizes in the orthorhombic space group Pna21, a = 13.644(4) Å, b = 12.934(4) Å, c = 6.992(2) Å, V = 1233.9(7) Å3, Z = 4, and d calc = 1.958 Mg/m3; R = 0.0316 and wR 2 = 0.0707 for 2630 reflections with I > 2σ(I). The molecular structure of TaCl(Me)(NMe2)3 consists of a trigonal bipyramidal core and contains axial and equatorial chlorine and methyl groups, respectively. ZnCl2(NHMe2)2 crystallizes in the orthorhombic space group P212121, a = 5.759(1) Å, b = 10.810(2) Å, c = 15.174(3) Å, V = 944.1(3) Å3, Z = 4, d calc = 1.593 Mg/m3; R = 0.0213 and wR 2 = 0.0494 for 1872 reflections with I > 2σ(I). ZnCl2(NHMe 2)2 exhibits a tetrahedral motif and represents the first reported four-coordinate zinc(II) compound containing acyclic monodentate secondary amine groups. The reaction between TaCl(NMe2)4 and MeMgCl afforded a mixture of tantalum products, of which TaCl(Me)(NMe 2)3 and Ta(NMe2)5 were found as the major products by 1H NMR spectroscopy.

AB - Treatment of TaCl(NMe2)4 with ZnMe2 in pentane furnishes a mixture of TaCl(Me)(NMe2)3, TaMe(NMe2)4, and Ta(NMe2)5 as the principal reaction products based on 1H NMR spectroscopy. Depending upon the work-up conditions employed, the compounds TaCl(Me)(NMe 2)3 and ZnCl2(NHMe2)2 have been isolated and their molecular structures established by X-ray crystallography. TaCl(Me)(NMe2)3 crystallizes in the orthorhombic space group Pna21, a = 13.644(4) Å, b = 12.934(4) Å, c = 6.992(2) Å, V = 1233.9(7) Å3, Z = 4, and d calc = 1.958 Mg/m3; R = 0.0316 and wR 2 = 0.0707 for 2630 reflections with I > 2σ(I). The molecular structure of TaCl(Me)(NMe2)3 consists of a trigonal bipyramidal core and contains axial and equatorial chlorine and methyl groups, respectively. ZnCl2(NHMe2)2 crystallizes in the orthorhombic space group P212121, a = 5.759(1) Å, b = 10.810(2) Å, c = 15.174(3) Å, V = 944.1(3) Å3, Z = 4, d calc = 1.593 Mg/m3; R = 0.0213 and wR 2 = 0.0494 for 1872 reflections with I > 2σ(I). ZnCl2(NHMe 2)2 exhibits a tetrahedral motif and represents the first reported four-coordinate zinc(II) compound containing acyclic monodentate secondary amine groups. The reaction between TaCl(NMe2)4 and MeMgCl afforded a mixture of tantalum products, of which TaCl(Me)(NMe 2)3 and Ta(NMe2)5 were found as the major products by 1H NMR spectroscopy.

KW - Crystallography

KW - Metal amides

KW - Organometallics

KW - Tantalum compounds

KW - Zinc compounds

UR - http://www.scopus.com/inward/record.url?scp=77951206013&partnerID=8YFLogxK

U2 - 10.1007/s10870-009-9630-0

DO - 10.1007/s10870-009-9630-0

M3 - Article

AN - SCOPUS:77951206013

SN - 1074-1542

VL - 40

SP - 173

EP - 178

JO - Journal of Chemical Crystallography

JF - Journal of Chemical Crystallography

IS - 2

ER -