Synthesis and Reactivity of New 2-[P,N]Pt(II) Complexes of Diisopropylphosphino-Substituted 2-Dimethylamino
详细信息 查看全文
- 作者：Bradley M. Wile ; Robert McDonald ; Michael J. Ferguson ; and Mark Stradiotto
- 刊名：Organometallics
- 出版年：2005
- 出版时间：April 11, 2005
- 年：2005
- 卷：24
- 期：8
- 页码：1959 - 1965
- 全文大小：146K
- 年卷期：v.24,no.8(April 11, 2005)
- ISSN：1520-6041
文摘
Treatment of 1-PiPr2-2-NMe2-indene (1a[H]) with either cis/trans-(SMe2)2PtCl2 or PtCl2provided (
2-P,N-2-NMe2-3-PiPr2-indene)PtCl2 (2) in 84% and 55% yield, respectively, whilethe reaction of 1a[H] with (
4-COD)PtClMe afforded (2-P,N-2-NMe2-3-PiPr2-indene)PtClMe(3) in 91% yield. Whereas in the formation of 2 and 3 the ligand precursor 1a[H] undergoesa rearrangement to give a coordinated 2-NMe2-3-PiPr2-indene (1b[H]) ligand, 1a[H] reactedcleanly with 0.5 equiv of [(
-SMe2)PtMe2]2 to give (2-P,N-1a[H])PtMe2 (4a) in 97% yield.The isomerization of 4a to (2-P,N-1b[H])PtMe2 (4b) in a THF/iPrOH mixture is rapid andallowed for the isolation of 4b in 99% yield. Heating of 4a in CH2Cl2 resulted in thequantitative formation of 3, while the thermolysis of 4a in toluene in the presence of SMe2afforded 5, the apparent product of intramolecular C-H activation of an NMe group. Thereactivity of 4a with a variety of other two-electron donors, as well as E-H-containingsubstrates (E = main group fragment), is reported. Although NMR spectroscopic evidenceindicated the formation of an intermediate of the type (2-P,N-1[H])Pt(SnPh3)(Me), as wellas Ph6Sn2, in the reaction of 4a with 10 equiv of Ph3SnH, negligible conversion of Ph3SnHto Ph6Sn2 was obtained when employing 1 mol % 4a as a catalyst. Single-crystal X-raydiffraction data for 2 and 5 are reported.
2-P,N-2-NMe2-3-PiPr2-indene)PtCl2 (2) in 84% and 55% yield, respectively, whilethe reaction of 1a[H] with (4-COD)PtClMe afforded (2-P,N-2-NMe2-3-PiPr2-indene)PtClMe(3) in 91% yield. Whereas in the formation of 2 and 3 the ligand precursor 1a[H] undergoesa rearrangement to give a coordinated 2-NMe2-3-PiPr2-indene (1b[H]) ligand, 1a[H] reactedcleanly with 0.5 equiv of [(-SMe2)PtMe2]2 to give (2-P,N-1a[H])PtMe2 (4a) in 97% yield.The isomerization of 4a to (2-P,N-1b[H])PtMe2 (4b) in a THF/iPrOH mixture is rapid andallowed for the isolation of 4b in 99% yield. Heating of 4a in CH2Cl2 resulted in thequantitative formation of 3, while the thermolysis of 4a in toluene in the presence of SMe2afforded 5, the apparent product of intramolecular C-H activation of an NMe group. Thereactivity of 4a with a variety of other two-electron donors, as well as E-H-containingsubstrates (E = main group fragment), is reported. Although NMR spectroscopic evidenceindicated the formation of an intermediate of the type (2-P,N-1[H])Pt(SnPh3)(Me), as wellas Ph6Sn2, in the reaction of 4a with 10 equiv of Ph3SnH, negligible conversion of Ph3SnHto Ph6Sn2 was obtained when employing 1 mol % 4a as a catalyst. Single-crystal X-raydiffraction data for 2 and 5 are reported.