Reactivity of OsH2Cl2(PiPr3)2 toward Diolefins: New Reactions Involving C-H and C-C Activation and C-C and C-P Bond Formation Processes
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- 作者：Andrew J. Edwards ; Miguel A. Esteruelas ; Fernando J. Lahoz ; Ana M. Ló ; pez ; Enrique Oñ ; ate ; Luis A. Oro ; and José ; I. Tolosa
- 刊名：Organometallics
- 出版年：1997
- 出版时间：March 18, 1997
- 年：1997
- 卷：16
- 期：6
- 页码：1316 - 1325
- 全文大小：331K
- 年卷期：v.16,no.6(March 18, 1997)
- ISSN：1520-6041
文摘
The dihydrido-dichloro complexOsH2Cl2(PiPr3)2(1) reacts with 1,5-cyclooctadiene in tolueneunder reflux to give the isopropenylphosphine derivativeOsCl2(
4-COD){[2-CH2=C(CH3)]PiPr2} (2), which has been characterized by X-raydiffraction analysis. The coordinationgeometry around the osmium atom of 2 can be rationalized asa highly distorted octahedron.The distortion is due to the ring constraint imposed by thebidentate isopropenylphosphineligand, which acts with a bite angle of 56.0(1)
. Intoluene at 85 C, the reaction of 1 with1,5-cyclooctadiene leads to the hydrido compoundOsHCl2(4-C8H11PiPr3)(PiPr3)(3). Themolecular structure of this complex has also been determined by anX-ray investigation.The X-ray diffraction analysis of 3 demonstrates the4-binding mode of the carbocyclic ligand[C8H11PiPr3]+.The coordination geometry around the osmium center can berationalized asa distorted octahedron with the triisopropylphosphine, a chlorine atom,and the carbocyclicligand forming the equatorial plane. Complex 3 reactswith 1,5-cyclooctadiene and 2,5-norbornadiene (NBD) to give 2 andOsCl2(4-NBD){[2-CH2=C(CH3)]PiPr2}(8), respectively.Complex 8 can also be obtained, under refluxingtoluene, from 1 and 2,5-norbornadiene.Similarly, the reaction of 1 withtetrafluorobenzobarrelene (TFB) affords a mixture of thepropenylphosphine isomersOsCl2(4-TFB){(2-CH2=CHCH2)PiPr2}(9) andOsCl2(4-TFB){[2-CH2=C(CH3)]PiPr2}(10), which can also be prepared from 3 andtetrafluorobenzobarrelene.The molecular structure of 9 has been determined byX-ray diffraction analysis. Thecoordination geometry around the osmium can be described as a distortedoctahedron, andas for 2, the distortion is mainly due to the ringconstraint imposed by the bidentate olefin-phosphine ligand, which in this case acts with a bite angle of74.8(1).
4-COD){[2-CH2=C(CH3)]PiPr2} (2), which has been characterized by X-raydiffraction analysis. The coordinationgeometry around the osmium atom of 2 can be rationalized asa highly distorted octahedron.The distortion is due to the ring constraint imposed by thebidentate isopropenylphosphineligand, which acts with a bite angle of 56.0(1). Intoluene at 85 C, the reaction of 1 with1,5-cyclooctadiene leads to the hydrido compoundOsHCl2(4-C8H11PiPr3)(PiPr3)(3). Themolecular structure of this complex has also been determined by anX-ray investigation.The X-ray diffraction analysis of 3 demonstrates the4-binding mode of the carbocyclic ligand[C8H11PiPr3]+.The coordination geometry around the osmium center can berationalized asa distorted octahedron with the triisopropylphosphine, a chlorine atom,and the carbocyclicligand forming the equatorial plane. Complex 3 reactswith 1,5-cyclooctadiene and 2,5-norbornadiene (NBD) to give 2 andOsCl2(4-NBD){[2-CH2=C(CH3)]PiPr2}(8), respectively.Complex 8 can also be obtained, under refluxingtoluene, from 1 and 2,5-norbornadiene.Similarly, the reaction of 1 withtetrafluorobenzobarrelene (TFB) affords a mixture of thepropenylphosphine isomersOsCl2(4-TFB){(2-CH2=CHCH2)PiPr2}(9) andOsCl2(4-TFB){[2-CH2=C(CH3)]PiPr2}(10), which can also be prepared from 3 andtetrafluorobenzobarrelene.The molecular structure of 9 has been determined byX-ray diffraction analysis. Thecoordination geometry around the osmium can be described as a distortedoctahedron, andas for 2, the distortion is mainly due to the ringconstraint imposed by the bidentate olefin-phosphine ligand, which in this case acts with a bite angle of74.8(1).