Use of alkane elimination in the one-step synthesis of organoscandium complexes containing a new multidentate cyclopentadienyl ligand

Ying Mu; Warren E. Piers; Donald C. MacQuarrie; Michael J. Zaworotko; Victor G. Young

doi:10.1021/om9600856

Use of alkane elimination in the one-step synthesis of organoscandium complexes containing a new multidentate cyclopentadienyl ligand

Ying Mu, Warren E. Piers, Donald C. MacQuarrie, Michael J. Zaworotko, Victor G. Young

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

Abstract

A new multidentate ligand, CpH^NMeSiN(H)R (SiNR = -SiMe₂N-tert-butyl; NMe = 3-CH₂-CH₂NMe₂; 1) was prepared in 71% yield as a mixture of 1,3 and 1,2 isomers (≈7:3) in one step from CpH^NMe, Me₂SiCl₂, and tert-butylamine. The ligand was attached to scandium in an efficient alkane elimination reaction by treatment of in situ generated Sc(CH₂SiMe₃)₃·-2THF with diproteo 1, yielding the alkylscandium species [(Cp^NMeSiNR)Sc(CH₂SiMe₃)], 2, directly in 52% yield. The reaction was 100% diastereoselective for the (1S)-(R_Sc)/(1R)-(S_Sc) pair of enantiomers. Treatment of 2 with dihydrogen gave two of four possible diastereomeric μ-dihydrides. The C_i symmetric R1-trans-1′S diasteriomer 3a was characterized crystallographically. Thermolysis of 2 at 70 °C for 3 days resulted in metalation of an N-methyl group and loss of Me₄Si. A mixture of two dimeric compounds with bridging methylene units was formed, one of which was identified as the C_i symmetric 1R-trans-1′S diasteriomer 4a by X-ray crystallography.

Original language	English
Pages (from-to)	2720-2726
Number of pages	7
Journal	Organometallics
Volume	15
Issue number	12
DOIs	https://doi.org/10.1021/om9600856
Publication status	Published - 11 Jun 1996
Externally published	Yes

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@article{653ae3e9735240e1a32ab5e6ec642320,

title = "Use of alkane elimination in the one-step synthesis of organoscandium complexes containing a new multidentate cyclopentadienyl ligand",

abstract = "A new multidentate ligand, CpHNMeSiN(H)R (SiNR = -SiMe2N-tert-butyl; NMe = 3-CH2-CH2NMe2; 1) was prepared in 71% yield as a mixture of 1,3 and 1,2 isomers (≈7:3) in one step from CpHNMe, Me2SiCl2, and tert-butylamine. The ligand was attached to scandium in an efficient alkane elimination reaction by treatment of in situ generated Sc(CH2SiMe3)3·-2THF with diproteo 1, yielding the alkylscandium species [(CpNMeSiNR)Sc(CH2SiMe3)], 2, directly in 52% yield. The reaction was 100% diastereoselective for the (1S)-(RSc)/(1R)-(SSc) pair of enantiomers. Treatment of 2 with dihydrogen gave two of four possible diastereomeric μ-dihydrides. The Ci symmetric R1-trans-1′S diasteriomer 3a was characterized crystallographically. Thermolysis of 2 at 70 °C for 3 days resulted in metalation of an N-methyl group and loss of Me4Si. A mixture of two dimeric compounds with bridging methylene units was formed, one of which was identified as the Ci symmetric 1R-trans-1′S diasteriomer 4a by X-ray crystallography.",

author = "Ying Mu and Piers, {Warren E.} and MacQuarrie, {Donald C.} and Zaworotko, {Michael J.} and Young, {Victor G.}",

year = "1996",

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doi = "10.1021/om9600856",

language = "English",

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T1 - Use of alkane elimination in the one-step synthesis of organoscandium complexes containing a new multidentate cyclopentadienyl ligand

AU - Mu, Ying

AU - Piers, Warren E.

AU - MacQuarrie, Donald C.

AU - Zaworotko, Michael J.

AU - Young, Victor G.

PY - 1996/6/11

Y1 - 1996/6/11

N2 - A new multidentate ligand, CpHNMeSiN(H)R (SiNR = -SiMe2N-tert-butyl; NMe = 3-CH2-CH2NMe2; 1) was prepared in 71% yield as a mixture of 1,3 and 1,2 isomers (≈7:3) in one step from CpHNMe, Me2SiCl2, and tert-butylamine. The ligand was attached to scandium in an efficient alkane elimination reaction by treatment of in situ generated Sc(CH2SiMe3)3·-2THF with diproteo 1, yielding the alkylscandium species [(CpNMeSiNR)Sc(CH2SiMe3)], 2, directly in 52% yield. The reaction was 100% diastereoselective for the (1S)-(RSc)/(1R)-(SSc) pair of enantiomers. Treatment of 2 with dihydrogen gave two of four possible diastereomeric μ-dihydrides. The Ci symmetric R1-trans-1′S diasteriomer 3a was characterized crystallographically. Thermolysis of 2 at 70 °C for 3 days resulted in metalation of an N-methyl group and loss of Me4Si. A mixture of two dimeric compounds with bridging methylene units was formed, one of which was identified as the Ci symmetric 1R-trans-1′S diasteriomer 4a by X-ray crystallography.

AB - A new multidentate ligand, CpHNMeSiN(H)R (SiNR = -SiMe2N-tert-butyl; NMe = 3-CH2-CH2NMe2; 1) was prepared in 71% yield as a mixture of 1,3 and 1,2 isomers (≈7:3) in one step from CpHNMe, Me2SiCl2, and tert-butylamine. The ligand was attached to scandium in an efficient alkane elimination reaction by treatment of in situ generated Sc(CH2SiMe3)3·-2THF with diproteo 1, yielding the alkylscandium species [(CpNMeSiNR)Sc(CH2SiMe3)], 2, directly in 52% yield. The reaction was 100% diastereoselective for the (1S)-(RSc)/(1R)-(SSc) pair of enantiomers. Treatment of 2 with dihydrogen gave two of four possible diastereomeric μ-dihydrides. The Ci symmetric R1-trans-1′S diasteriomer 3a was characterized crystallographically. Thermolysis of 2 at 70 °C for 3 days resulted in metalation of an N-methyl group and loss of Me4Si. A mixture of two dimeric compounds with bridging methylene units was formed, one of which was identified as the Ci symmetric 1R-trans-1′S diasteriomer 4a by X-ray crystallography.

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DO - 10.1021/om9600856

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JO - Organometallics

JF - Organometallics

IS - 12

ER -

Use of alkane elimination in the one-step synthesis of organoscandium complexes containing a new multidentate cyclopentadienyl ligand

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