Intermediates in associative phosphine substitution reactions of (η5-C5H5)W(CO)2(NO) |
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| Authors: | Charles P Casey William D Jones Stephen G Harsy |
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| Institution: | Samuel M. McElvain Laboratories of Organic Chemistry, Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706 U.S.A. |
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| Abstract: | The reaction of (η5-C5H5)W(CO)2(NO), 6W, with P(CH3)3 proceeds rapidly at 25°C to give (η5-C5H5)W(CO)(NO)P(CH3)3], 7W. The rate of formation of 7W was found to be 4.48 × 10?2M?1 6W] P(CH3)3] at 25.0°c in THF. In neat P(CH3)3 at ?23°C, 6W is converted to (η1-C5H5)W(CO)2(NO)P(CH3)3]2, 8W. In dilute solution, 8W decomposes to initially give a 2:1 mixture of 6W and 7W. The mixture is then converted to 7W. The reaction of (η5-C5H5)Mo(CO)(NO), 6Mo, with P(CH3)3 is 6.1 times faster than that of the tungsten analog. |
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