Übergangsmetall‐phosphin‐Komplexe, IV. Über Cyclopentadienyl‐tricarbonyl‐phosphin‐vanadin(I), Cyclopentadientyl‐dicarbonyl‐phosphin‐mangan(I), Monophosphin‐pentacarbonyl‐Komplexe von Chrom, Molybdän und Wolfram sowie Tetracarbonyl‐phosphin‐eisen(0)

Abstract

Es wird uber Darstellungsmethoden, Eigenschaften, 1R-und 1H-NMR-Spektren der diamagnetischen, sublimierbaren Monophosphin -cyclopentadienyl-carbonyl -Komplexe C S H~V ( C O )~P H~ und CsH5Mn(CO)zPH3 sowie der Monophosphin-carbonyl-Komplexe Cr(C0)5PH3, Mo(CO)sPH3 W(C0)5PH3 und Fe(C0)4PH3 berichtet. Die Massenspektren der Verbindungen werden angegeben und diskutiert.Vor einiger Zeit isolierten wir die ersten Cyclopentadienyl-carbonyl-phosphinund Carbonyl-phosphin-Komplexe von Ubergangsmetallen2). Nachfolgend sei nunmehr ausfiihrlicher iiber Darstellung und Eigenschaften von CSHSV(CO)~PH~, C5HsMn(CO)zPH3, Cr(CO)SPH3, Mo(CO)sPH3, W(C0)5PH3 und Fe(C0)4PH3, den ersten bekannt gewordenen Vertretern dieser neuen Klasse von Verbindungen, berichtet.Bei der Umsetzung von Methylmethoxycarben-pentacarbonyl-chrom(0) mit PH3 hatten wir die Bildung von Methylphosphinocarben-pentacarbonyl-chrom(0) erhofft, falls sich PH3 analog NH3 verhielt, das nach (1) p C H 3 p H 2 (CO),Cr =C,Cr(C0)4(PH3)2 1 reagiert3). Statt dessen war gelbes, recht bestandiges Bis-phosphin-tetracarbonylchrom(0) (1) entstanden. Als offensichtlich iiberraschend gut zur dx-dx-Ruckbindung geeigneter Ligand hatte PH3 also einen CO-Liganden und den gesamten Carbenrest substituiert, wahrend NH3 nur dessen OCH3-Gruppe zu aminolysieren vermag. Wir haben uber das cis-konfigurierte 1 sowie dessen Mo-und W-Homologe, die un-

Nature of the Metal−Ligand Bond in M(CO)5PX3 Complexes (M = Cr, Mo, W; X = H, Me, F, Cl): Synthesis, Molecular Structure, and Quantum-Chemical Calculations

“…Syntheses. The phosphane complexes M(CO) 5 PH 3 and M(CO) 5 PF 3 (M = Cr, Mo, W) have been prepared earlier either by photochemical , or by thermal substitution from the metal hexacarbonyls and the ligands as precursors. As a rule, labile compounds such as M(CO) 5 (THF) and M(CO) 5 (CH 2 Cl 2 ) were used as intermediates.…”

“…To gain a better insight into the M−P bond description, further information resulting from advanced theoretical calculations and additional structural data are necessary. Of particularly great help would be the structure determination of the parent complexes M(CO) 5 PH 3 (M = Cr, Mo, W), which have been known from the work of Fischer and co-workers for about 30 years. Therefore, we have put considerable effort into the preparation of some representatives and into the isolation of suitable single crystals for X-ray diffraction studies.…”

[(CO)4W(PH3)2] as a Source of Semi-interstitial Phosphorus Ligands in Cobalt Carbonyl Clusters

“…PH 3 -functionalized complexes have been known since 1986, when Fischer synthesized the first PH 3 complex, [(CO) 4 M(PH 3 ) 2 ] (M = Cr, Mo, W), accidentally, by the reaction of [(CO) 5 M(C(OCH 3 )CH 3 )] with PH 3 , in order to obtain the P analogue complex of [(CO) 5 M(C(NH 2 )CH 3 )] . Afterwards, many attempts have been made to synthesize transition metal complexes of the general formulas [(CO) x M(PH 3 ) 6− x ] ( x = 3, 4, 5). − …”

Reactions of phosphine, arsine, and stibine with carbonylbis(triethylphosphine)iridium(I) halides. Part 1. Reactions in toluene; X-ray crystal structures of [Ir(CO)ClH(PEt3)2(AsH2)] and [Ir(CO)XH(PEt3)2(µ-ZH2)RuCl2(η6-MeC6H4CHMe2-p)](X = Br, Z = P; X = Cl, Z = As)

“…When proton coupling was restored, the lowfrequency resonance showed additional wide triplet couplings ['J(P'H) = 172. 4 Hz] and narrow doublet ['J(P'H) = 7. 3 Hz].…”