| Autor: |
Mark J M, Vlaar, Sander G A, van Assema, Frans J J, de Kanter, Marius, Schakel, Anthony L, Spek, Martin, Lutz, Koop, Lammertsma |
| Rok vydání: |
2002 |
| Zdroj: |
Chemistry (Weinheim an der Bergstrasse, Germany). 8(1) |
| ISSN: |
0947-6539 |
| Popis: |
Heating the nonchelating cis-bis-7-phosphanorbornadiene-[Mo(CO)4] complex (13) results in the thermal decomposition of one of the 7-phosphanorbornadiene groups. The phosphinidene thus generated adds intramolecularly to a C=C bond of the other ligand to give the novel diphosphorus complex 14. This reaction constitutes a metal-template-directed synthesis. Likewise, the intramolecular phosphinidene addition to the C=C bond of a Mo-phospholene ligand affords the diphos complex 18. Its crystal structure exhibits an extremely small P-Mo-P bite-angle for a five-membered chelate ring. The similar intramolecular 1,2-addition to a C=C bond of a phosphole ligand gives a highly strained, unstable intermediate product. Scission of its P-Mo bond generates a free coordination site, which is then occupied by either CO or a phosphole to yield complexes 22 and 23, respectively. The analogous intermolecular addition of [PhPW(CO)5] to a [phosphole-W(CO)5] complex gives the di-[W(CO)5] complexed adduct 28. The directing effect of the metal on the intra- and intermolecular additions is discussed. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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