Carbonylation of ( sup t Bu sub 3 SiNH) sub 3 ZrH and X-ray structural study of ( sup t Bu sub 3 SiNH) sub 3 ZrCH sub 3
Journal Article
·
· Organometallics; (United States)
- Cornell Univ., Ithaca, NY (United States)
Treatment of ZrCl{sub 4} with 3 equiv of {sup t}Bu{sub 3}SiNHLi afforded ({sup t}Bu{sub 3}SiNH){sub 3}ZrCl (1); alkylation of 1 with MeMgBr gave ({sup t}Bu{sub 3}SiNH){sub 3}ZrMe (2), whose structure was determined via X-ray crystallography. Crystal data: monoclinic, P2{sub 1}/c, a = 22.052 (3) {angstrom}, b = 12.943 (2) {angstrom}, c = 17.320 (2) {angstrom}, {beta} = 108.93 (1){degree}, Z = 4, T = 25C. The methyl derivative 2 exhibits near-tetrahedral coordination with a normal Zr-C distance (2.231 (7) {angstrom}) and virtually indistinguishable amido groups (d(Zr-N){sub av} = 2.039 (7) {angstrom}, {angle}(Zr-N-Si){sub av} = 151.4 (8){degree}). Upon thermolysis of 2 in cyclohexane (95C, 8 h), CH{sub 4} was eliminated via abstraction of an amido hydrogen, generating the transient (({sup t}Bu{sub 3}SiNH){sub 2}Zr{double bond}NSi{sup t}Bu{sub 3}) (3), which was scavenged by H{sub 2} (3 atm) to produce ({sup t}Bu{sub 3}SiNH){sub 3}ZrH (4). The monohydride 4 was shown to reduce CO to provide (({sup t}Bu{sub 3}SiNH){sub 3}Zr){sub 2}({mu}-OCH){sub 2} (6), presumably via monohydride (4) reduction of undetected (({sup t}Bu{sub 3}SiNH){sub 3}Zr(CHO)) (5). Further carbonylation yielded the spectroscopically observable (({sup t}Bu{sub 3}SiNH){sub 3}Zr){sub 2}({mu}-{eta}{sup 1}:{eta}{sup 2}-OCH{sub 2}C{double bond}O) (7) and, ultimately, (({sup t}Bu{sub 3}SiNH){sub 3}Zr){sub 2}(cis-{mu}-O(H)C{double bond}C(H)O) (8). Thermolysis of 6 in THF resulted in the elimination of ({sup t}Bu{sub 3}SiNH){sub 3}ZrOMe (10), leaving the transient 3, which was trapped by solvent to give ({sup t}Bu{sub 3}SiNH){sub 2}(THF)Zr{double bond}NSi{sup t}Bu{sub 3} (9). The addition of LiOMe to 1 provided an alternate route to 10. The mechanism of CO reduction is discussed in relation to other group 4 actinide mono- and dihydride systems.
- OSTI ID:
- 6106329
- Journal Information:
- Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 10:1; ISSN 0276-7333; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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OSTI ID:6769983
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OSTI ID:416518
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Related Subjects
01 COAL, LIGNITE, AND PEAT
010408 -- Coal
Lignite
& Peat-- C1 Processes-- (1987-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALINE EARTH METAL COMPOUNDS
BOND ANGLE
BOND LENGTHS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLATION
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMICAL SHIFT
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
DIMENSIONS
FISCHER-TROPSCH SYNTHESIS
GRIGNARD REAGENTS
HALIDES
HALOGEN COMPOUNDS
INFRARED SPECTRA
KINETICS
LENGTH
MAGNESIUM COMPOUNDS
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION INTERMEDIATES
REACTION KINETICS
SCATTERING
SPECTRA
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
ZIRCONIUM CHLORIDES
ZIRCONIUM COMPLEXES
ZIRCONIUM COMPOUNDS
010408 -- Coal
Lignite
& Peat-- C1 Processes-- (1987-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALINE EARTH METAL COMPOUNDS
BOND ANGLE
BOND LENGTHS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLATION
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMICAL SHIFT
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
DIMENSIONS
FISCHER-TROPSCH SYNTHESIS
GRIGNARD REAGENTS
HALIDES
HALOGEN COMPOUNDS
INFRARED SPECTRA
KINETICS
LENGTH
MAGNESIUM COMPOUNDS
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION INTERMEDIATES
REACTION KINETICS
SCATTERING
SPECTRA
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
ZIRCONIUM CHLORIDES
ZIRCONIUM COMPLEXES
ZIRCONIUM COMPOUNDS