Preparation of volatile molecular lithium-niobium alkoxides. Crystal structures of [Nb(μ-OCH2SiMe3)(OCH2SiMe3) 4]2 and [LiNb(μ3-OCH2SiMe3)-(μ 2-OCH2SiMe3)2(OCH 2SiMe3)3]2

Subhash C. Goel; Jennifer Ann Hollingsworth; Alicia M. Beatty; Kerry D. Robinson; William E. Buhro

doi:10.1016/S0277-5387(97)00311-2

Preparation of volatile molecular lithium-niobium alkoxides. Crystal structures of [Nb(μ-OCH₂SiMe₃)(OCH₂SiMe₃) ₄]₂ and [LiNb(μ₃-OCH₂SiMe₃)-(μ ₂-OCH₂SiMe₃)₂(OCH ₂SiMe₃)₃]₂

Subhash C. Goel
, Jennifer Ann Hollingsworth
, Alicia M. Beatty
, Kerry D. Robinson
, William E. Buhro

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

21 Scopus citations

Abstract

New heterometallic alkoxides [LiNb(OCH₂CMe₃)₆]₂ (4), LiNb(OCH₂CMe₃)₆(Me₃CCH ₂OH)₂ (5), and [LiNb(OCH₂SiMe₃)₆]₂ (6) have been prepared from the corresponding homometallic alkoxides. All are moderately soluble in hydrocarbons and sublime in moderate to good recoveries. The structure of 6 determined crystallographically contains an Nb₂Li₂(μ-O)₄(μ₃-O)₂ central-core geometry. Compound 4 appears to be isostructural on the basis of ¹H NMR data. Bulk pyrolysis of 4 gives crystalline LiNbO₃ under N₂ at 600 C. However, LiNbO₃ films are not obtained from 4 by spray MOCVD under conditions that give LiNbO₃ films from [LiNb(OEt)₆]∝. Crystallographic structure determination for the precursor compound [Nb(μ-OCH₂SiMe₃)(OCH₂SiMe₃) ₄]₂ (3) reveals an edge-shared bioctahedral geometry in which the μ-O atoms are distinctly pyramidal. This structure is maintained in solution; the pyramidal bridge configurations allow coexistence of syn and anti dimeric isomers. Precursor 3 also exhibits a dimer-monomer equilibrium for which ΔH = 63(3) kJ/mol and ΔS = 180(10) J/(K mol).

Original language	English
Pages (from-to)	781-790
Number of pages	10
Journal	Polyhedron
Volume	17
Issue number	5-6
DOIs	https://doi.org/10.1016/S0277-5387(97)00311-2
State	Published - Jan 1 1998
Externally published	Yes

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10.1016/S0277-5387(97)00311-2

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@article{38f082b0cf97455ab84b036aeceb2334,

title = "Preparation of volatile molecular lithium-niobium alkoxides. Crystal structures of [Nb(μ-OCH2SiMe3)(OCH2SiMe3) 4]2 and [LiNb(μ3-OCH2SiMe3)-(μ 2-OCH2SiMe3)2(OCH 2SiMe3)3]2",

abstract = "New heterometallic alkoxides [LiNb(OCH2CMe3)6]2 (4), LiNb(OCH2CMe3)6(Me3CCH 2OH)2 (5), and [LiNb(OCH2SiMe3)6]2 (6) have been prepared from the corresponding homometallic alkoxides. All are moderately soluble in hydrocarbons and sublime in moderate to good recoveries. The structure of 6 determined crystallographically contains an Nb2Li2(μ-O)4(μ3-O)2 central-core geometry. Compound 4 appears to be isostructural on the basis of 1H NMR data. Bulk pyrolysis of 4 gives crystalline LiNbO3 under N2 at 600 C. However, LiNbO3 films are not obtained from 4 by spray MOCVD under conditions that give LiNbO3 films from [LiNb(OEt)6]∝. Crystallographic structure determination for the precursor compound [Nb(μ-OCH2SiMe3)(OCH2SiMe3) 4]2 (3) reveals an edge-shared bioctahedral geometry in which the μ-O atoms are distinctly pyramidal. This structure is maintained in solution; the pyramidal bridge configurations allow coexistence of syn and anti dimeric isomers. Precursor 3 also exhibits a dimer-monomer equilibrium for which ΔH = 63(3) kJ/mol and ΔS = 180(10) J/(K mol).",

author = "Goel, \{Subhash C.\} and Hollingsworth, \{Jennifer Ann\} and Beatty, \{Alicia M.\} and Robinson, \{Kerry D.\} and Buhro, \{William E.\}",

year = "1998",

month = jan,

day = "1",

doi = "10.1016/S0277-5387(97)00311-2",

language = "English",

volume = "17",

pages = "781--790",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd.",

number = "5-6",

}

Preparation of volatile molecular lithium-niobium alkoxides. Crystal structures of [Nb(μ-OCH₂SiMe₃)(OCH₂SiMe₃) ₄]₂ and [LiNb(μ₃-OCH₂SiMe₃)-(μ ₂-OCH₂SiMe₃)₂(OCH ₂SiMe₃)₃]₂. / Goel, Subhash C.; Hollingsworth, Jennifer Ann; Beatty, Alicia M. et al.
In: Polyhedron, Vol. 17, No. 5-6, 01.01.1998, p. 781-790.

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

TY - JOUR

T1 - Preparation of volatile molecular lithium-niobium alkoxides. Crystal structures of [Nb(μ-OCH2SiMe3)(OCH2SiMe3) 4]2 and [LiNb(μ3-OCH2SiMe3)-(μ 2-OCH2SiMe3)2(OCH 2SiMe3)3]2

AU - Goel, Subhash C.

AU - Hollingsworth, Jennifer Ann

AU - Beatty, Alicia M.

AU - Robinson, Kerry D.

AU - Buhro, William E.

PY - 1998/1/1

Y1 - 1998/1/1

N2 - New heterometallic alkoxides [LiNb(OCH2CMe3)6]2 (4), LiNb(OCH2CMe3)6(Me3CCH 2OH)2 (5), and [LiNb(OCH2SiMe3)6]2 (6) have been prepared from the corresponding homometallic alkoxides. All are moderately soluble in hydrocarbons and sublime in moderate to good recoveries. The structure of 6 determined crystallographically contains an Nb2Li2(μ-O)4(μ3-O)2 central-core geometry. Compound 4 appears to be isostructural on the basis of 1H NMR data. Bulk pyrolysis of 4 gives crystalline LiNbO3 under N2 at 600 C. However, LiNbO3 films are not obtained from 4 by spray MOCVD under conditions that give LiNbO3 films from [LiNb(OEt)6]∝. Crystallographic structure determination for the precursor compound [Nb(μ-OCH2SiMe3)(OCH2SiMe3) 4]2 (3) reveals an edge-shared bioctahedral geometry in which the μ-O atoms are distinctly pyramidal. This structure is maintained in solution; the pyramidal bridge configurations allow coexistence of syn and anti dimeric isomers. Precursor 3 also exhibits a dimer-monomer equilibrium for which ΔH = 63(3) kJ/mol and ΔS = 180(10) J/(K mol).

AB - New heterometallic alkoxides [LiNb(OCH2CMe3)6]2 (4), LiNb(OCH2CMe3)6(Me3CCH 2OH)2 (5), and [LiNb(OCH2SiMe3)6]2 (6) have been prepared from the corresponding homometallic alkoxides. All are moderately soluble in hydrocarbons and sublime in moderate to good recoveries. The structure of 6 determined crystallographically contains an Nb2Li2(μ-O)4(μ3-O)2 central-core geometry. Compound 4 appears to be isostructural on the basis of 1H NMR data. Bulk pyrolysis of 4 gives crystalline LiNbO3 under N2 at 600 C. However, LiNbO3 films are not obtained from 4 by spray MOCVD under conditions that give LiNbO3 films from [LiNb(OEt)6]∝. Crystallographic structure determination for the precursor compound [Nb(μ-OCH2SiMe3)(OCH2SiMe3) 4]2 (3) reveals an edge-shared bioctahedral geometry in which the μ-O atoms are distinctly pyramidal. This structure is maintained in solution; the pyramidal bridge configurations allow coexistence of syn and anti dimeric isomers. Precursor 3 also exhibits a dimer-monomer equilibrium for which ΔH = 63(3) kJ/mol and ΔS = 180(10) J/(K mol).

UR - https://www.scopus.com/pages/publications/0000742868

U2 - 10.1016/S0277-5387(97)00311-2

DO - 10.1016/S0277-5387(97)00311-2

M3 - Article

SN - 0277-5387

VL - 17

SP - 781

EP - 790

JO - Polyhedron

JF - Polyhedron

IS - 5-6

ER -

Preparation of volatile molecular lithium-niobium alkoxides. Crystal structures of [Nb(μ-OCH2SiMe3)(OCH2SiMe3) 4]2 and [LiNb(μ3-OCH2SiMe3)-(μ 2-OCH2SiMe3)2(OCH 2SiMe3)3]2

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Preparation of volatile molecular lithium-niobium alkoxides. Crystal structures of [Nb(μ-OCH₂SiMe₃)(OCH₂SiMe₃) ₄]₂ and [LiNb(μ₃-OCH₂SiMe₃)-(μ ₂-OCH₂SiMe₃)₂(OCH ₂SiMe₃)₃]₂