Imido Complexes Derived from the Reactions of Niobium and Tantalum Pentachlorides with Primary Amines: Relevance to the Chemical Vapor Deposition of Metal Nitride Films
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- 作者：Kumudini C. Jayaratne ; Glenn P. A. Yap ; Brian S. Haggerty ; Arnold L. Rheingold ; and Charles H. Winter
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：August 14, 1996
- 年：1996
- 卷：35
- 期：17
- 页码：4910 - 4920
- 全文大小：276K
- 年卷期：v.35,no.17(August 14, 1996)
- ISSN：1520-510X
文摘
Reactions of niobium and tantalumpentachlorides with tert-butylamine (
6 equiv) in benzeneafford the dimericimido complexes[NbCl2(NtBu)(NHtBu)(NH2tBu)]2(90%) and[TaCl2(NtBu)(NHtBu)(NH2tBu)]2(79%). Theniobium complex exists as two isomers in solution, while the tantalumcomplex is composed of three majorisomers and at least two minor isomers. Analogous treatments withisopropylamine (7 equiv) give the monomericcomplexesNbCl2(NiPr)(NHiPr)(NH2iPr)2(84%) andTaCl2(NiPr)(NHiPr)(NH2iPr)2(84%). The monomericcomplexes are unaffected by treatment with excess isopropylamine, whilethe dimeric complexes are cleaved tothe monomersMCl2(NtBu)(NHtBu)(NH2tBu)2upon addition of excess tert-butylamine in chloroformsolution.Treatment of niobium and tantalum pentachlorides with2,6-diisopropylaniline affords insoluble precipitates of[NH3(2,6-(CH(CH3)2)2C6H3)]2[NbCl5(N(2,6-(CH(CH3)2)2C6H3))](100%) and[NH3(2,6-(CH(CH3)2)2C6H3)]2[TaCl5(N(2,6-(CH(CH3)2)2C6H3))](100%), which react with 4-tert-butylpyridine to afford thesoluble complexes [4-t-C4H9C5H4NH]2[NbCl5(N(2,6-(CH(CH3)2)2C6H3))](45%) and[4-t-C4H9C5H4NH]2[TaCl5(N(2,6-(CH(CH3)2)2C6H3))](44%). Sublimation of[NbCl2(NtBu)(NHtBu)(NH2tBu)]2,MCl2(NiPr)(NHiPr)(NH2iPr)2,and [NH3(2,6-(CH(CH3)2)2C6H3)]2[MCl5(N(2,6-(CH(CH3)2)2C6H3))]leads to decomposition to give[MCl3(NR)(NH2R)]2 assublimates(32-49%), leaving complexes of the proposed formulationMCl(NR)2 as nonvolatile residues. Bycontrast,[TaCl2(NtBu)(NHtBu)(NH2tBu)]2sublimes without chemical reaction. Analysis of the organicproducts obtainedfrom thermal decomposition of[NbCl2(NtBu)(NHtBu)(NH2tBu)]2showed isobutylene and tert-butylamine in a2.2:1 ratio. Mass spectra of[NbCl2(NtBu)(NHtBu)(NH2tBu)]2,[TaCl2(NtBu)(NHtBu)(NH2tBu)]2,and [NbCl3(NiPr)(NH2iPr)]2showed the presence of dimeric imido complexes, monomeric imidocomplexes, and nitridocomplexes, implying that such species are important gas phase speciesin CVD processes utilizing these molecularprecursors. The crystal structures of[4-t-C4H9C5H4NH]2[NbCl5(N(2,6-(CH(CH3)2)2C6H3))],[NbCl3(NiPr)(NH2iPr)]2,[NbCl3(N(2,6-(CH(CH3)2)2C6H3))(NH2(2,6-(CH(CH3)2)2C6H3))]2,and[TaCl3(N(2,6-(CH(CH3)2)2C6H3))(NH2(2,6-(CH(CH3)2)2C6H3))]2were determined.[4-t-C4H9C5H4NH]2[NbCl5(N(2,6-(CH(CH3)2)2C6H3))]crystallizesin the space group P21/c witha = 12.448(3) Å, b = 10.363(3) Å,c = 28.228(3) Å, 
= 94.92(1)
,V = 3628(5)Å3, and Z = 4.[NbCl3(NiPr)(NH2iPr)]2crystallizes in the space group P21/cwith a = 9.586(4) Å, b =12.385(4)Å, c = 11.695(4) Å, = 112.89(2),V = 1279.0(6) Å3, and Z =2.[NbCl3(N(2,6-(CH(CH3)2)2C6H3))(NH2(2,6-(CH(CH3)2)2C6H3))]2crystallizes in the space group P21/nwith a = 10.285(3) Å, b =11.208(3) Å, c =23.867(6) Å, = 97.53, V = 2727(1)Å3, and Z = 2.[TaCl3(N(2,6-(CH(CH3)2)2C6H3))(NH2(2,6-(CH(CH3)2)2C6H3))]2crystallizes in the space group P21/nwith a = 10.273(1) Å, b =11.241(2) Å, c = 23.929(7) Å, = 97.69(2), V = 2695(2)Å3, and Z = 2. These findings arediscussed in the context of niobium and tantalumnitride film depositions from molecular precursors.
6 equiv) in benzeneafford the dimericimido complexes[NbCl2(NtBu)(NHtBu)(NH2tBu)]2(90%) and[TaCl2(NtBu)(NHtBu)(NH2tBu)]2(79%). Theniobium complex exists as two isomers in solution, while the tantalumcomplex is composed of three majorisomers and at least two minor isomers. Analogous treatments withisopropylamine (7 equiv) give the monomericcomplexesNbCl2(NiPr)(NHiPr)(NH2iPr)2(84%) andTaCl2(NiPr)(NHiPr)(NH2iPr)2(84%). The monomericcomplexes are unaffected by treatment with excess isopropylamine, whilethe dimeric complexes are cleaved tothe monomersMCl2(NtBu)(NHtBu)(NH2tBu)2upon addition of excess tert-butylamine in chloroformsolution.Treatment of niobium and tantalum pentachlorides with2,6-diisopropylaniline affords insoluble precipitates of[NH3(2,6-(CH(CH3)2)2C6H3)]2[NbCl5(N(2,6-(CH(CH3)2)2C6H3))](100%) and[NH3(2,6-(CH(CH3)2)2C6H3)]2[TaCl5(N(2,6-(CH(CH3)2)2C6H3))](100%), which react with 4-tert-butylpyridine to afford thesoluble complexes [4-t-C4H9C5H4NH]2[NbCl5(N(2,6-(CH(CH3)2)2C6H3))](45%) and[4-t-C4H9C5H4NH]2[TaCl5(N(2,6-(CH(CH3)2)2C6H3))](44%). Sublimation of[NbCl2(NtBu)(NHtBu)(NH2tBu)]2,MCl2(NiPr)(NHiPr)(NH2iPr)2,and [NH3(2,6-(CH(CH3)2)2C6H3)]2[MCl5(N(2,6-(CH(CH3)2)2C6H3))]leads to decomposition to give[MCl3(NR)(NH2R)]2 assublimates(32-49%), leaving complexes of the proposed formulationMCl(NR)2 as nonvolatile residues. Bycontrast,[TaCl2(NtBu)(NHtBu)(NH2tBu)]2sublimes without chemical reaction. Analysis of the organicproducts obtainedfrom thermal decomposition of[NbCl2(NtBu)(NHtBu)(NH2tBu)]2showed isobutylene and tert-butylamine in a2.2:1 ratio. Mass spectra of[NbCl2(NtBu)(NHtBu)(NH2tBu)]2,[TaCl2(NtBu)(NHtBu)(NH2tBu)]2,and [NbCl3(NiPr)(NH2iPr)]2showed the presence of dimeric imido complexes, monomeric imidocomplexes, and nitridocomplexes, implying that such species are important gas phase speciesin CVD processes utilizing these molecularprecursors. The crystal structures of[4-t-C4H9C5H4NH]2[NbCl5(N(2,6-(CH(CH3)2)2C6H3))],[NbCl3(NiPr)(NH2iPr)]2,[NbCl3(N(2,6-(CH(CH3)2)2C6H3))(NH2(2,6-(CH(CH3)2)2C6H3))]2,and[TaCl3(N(2,6-(CH(CH3)2)2C6H3))(NH2(2,6-(CH(CH3)2)2C6H3))]2were determined.[4-t-C4H9C5H4NH]2[NbCl5(N(2,6-(CH(CH3)2)2C6H3))]crystallizesin the space group P21/c witha = 12.448(3) Å, b = 10.363(3) Å,c = 28.228(3) Å, = 94.92(1),V = 3628(5)Å3, and Z = 4.[NbCl3(NiPr)(NH2iPr)]2crystallizes in the space group P21/cwith a = 9.586(4) Å, b =12.385(4)Å, c = 11.695(4) Å, = 112.89(2),V = 1279.0(6) Å3, and Z =2.[NbCl3(N(2,6-(CH(CH3)2)2C6H3))(NH2(2,6-(CH(CH3)2)2C6H3))]2crystallizes in the space group P21/nwith a = 10.285(3) Å, b =11.208(3) Å, c =23.867(6) Å, = 97.53, V = 2727(1)Å3, and Z = 2.[TaCl3(N(2,6-(CH(CH3)2)2C6H3))(NH2(2,6-(CH(CH3)2)2C6H3))]2crystallizes in the space group P21/nwith a = 10.273(1) Å, b =11.241(2) Å, c = 23.929(7) Å, = 97.69(2), V = 2695(2)Å3, and Z = 2. These findings arediscussed in the context of niobium and tantalumnitride film depositions from molecular precursors.