Bidentate phosphorus baskets by intramolecular phosphinidene addition.
Intramolecular phosphinidene addition to the C==C bond of Mo-complexed, seven-membered phosphorus heterocycles affords three novel [(diphos)Mo(CO)(4)] complexes (18-20). The three bidentate phosphorus baskets differ in the composition of the seven-membered ring: one of the phosphorus atoms is flanked by CH(2), NCH(3), or O. The unsaturated tetrahydrophosphepine precursors are synthesized by either ring-closing metathesis (C and N derivatives) or by a cyclization sequence (O derivative). The crystal structures of the nitrogen- (19) and oxygen-containing (20) baskets have relatively small P-Mo-P angles of 76.240(13) degrees and 77.626(12) degrees , respectively, and complex 20 has slightly shortened Mo--P bond lengths.
van Assema
Sander G A
SG
Department of Organic and Inorganic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
Ehlers
Andreas W
AW
de Kanter
Frans J J
FJ
Schakel
Marius
M
Spek
Anthony L
AL
Lutz
Martin
M
Lammertsma
Koop
K
D008968:Molecular Conformation; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry; D010758:Phosphorus / Q000737:chemistry*
D009942:Organometallic Compounds; D010720:Phosphines; C521447:tetracarbonyl(3,5-dimethyl-4,8-diphenyl-3,5-diaza-4,8-diphosphabicyclo(5.1.0)octane)molybdenum; C521448:tetracarbonyl(4,8-diphenyl-3,5-dioxa-4,8-diphosphabicyclo(5.1.0)octane)molybdenum; C521446:tetracarbonyl(4,8-diphenyl-4,8-diphosphabicyclo(5.1.0)octane)molybdenum; D010758:Phosphorus; D008982:Molybdenum