Solid-state and solution structures of a series of [(HBPZ3 (Me2))Rh(CO)(PR3)] and [(HBPZ3Me2,4Cl)Rh(CO)(PR3)] complexes

Citation
F. Malbosc et al., Solid-state and solution structures of a series of [(HBPZ3 (Me2))Rh(CO)(PR3)] and [(HBPZ3Me2,4Cl)Rh(CO)(PR3)] complexes, EUR J INORG, (10), 2001, pp. 2689-2697
Citations number
27
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
ISSN journal
1434-1948 → ACNP
Issue
10
Year of publication
2001
Pages
2689 - 2697
Database
ISI
SICI code
1434-1948(200110):10<2689:SASSOA>2.0.ZU;2-N
Abstract
Addition of 1 equiv, of a phosphane or phosphite ligand to the kappa (3)-bo nded [Tp(Me2)Rh(CO)(2)] and [Tp(Me2,4Cl)Rh(CO)(2)] dicarbonyl precursors gi ves the monosubstituted complexes [TpRh(CO)L], The X-ray crystal structures show that the three complexes [Tp(Me2)Rh(CO)(PMe3)], [Tp(Me2)Rh(CO)(PMePh2 )], and [Tp(Me2,4Cl)Rh(CO)(PMePh2)] adopt square-planar geometries. The X-r ay crystal structure of [Tp(Me2)Rh(CO){P(OPh)(3)}] is consistent with an in teraction between the dangling pyrazolyl groups and the rhodium centre, the Rh-N distance being 2.762(3) Angstrom. Analysis of v(BH) and v(CO) stretch ing frequencies shows that all the phosphane-containing complexes are squar e planar in solution as well as in the solid state. According to infrared a nalyses, the phosphite complexes [Tp(Me2,4Cl)Rh(CO){P(OPh)(3)}] and [Tp(Me2 ,4Cl)Rh(CO){P(OMe)(3)}] adopt a pentacoordinated geometry both in the solid state and in solution. However, the infrared data for [Tp(Me2)Rh(CO){P(OPh )(3)}] and [Tp(Me2)Rh(CO){P(OMe)(3)}] indicate that the Tp(Me2) ligand is i n a kappa (3) coordination mode in the solid state, as already evidenced by the X-ray crystal structure, but in a kappa (2) mode in solution. We also describe an exchange phenomenon between dangling and coordinated pyrazolyl groups, as studied by NMR.