Dichlorotrinitrosylvanadin entsteht durch Umsetzung von VCl4mit NO in CCl4 bei 20°. Für [V(NO)3Cl2]n, das sich auch aus V(CO)6 und NOCl bildet, wird eine mehrkernige Struktur mit trigonal Pyramidaler V(NO)3‐Gruppe sowie mit endständigen V‐Cl‐Bindungen und V‐Cl‐V‐Brücken vorgeschlagen. [V(NO)3Cl2]n setzt sich unter milden Bedingungen mit N‐ und O‐Basen unter Substitution von zwei NO‐Liganden zu Mononitrosylkomplexen V(NO)LnCl2 um. Mit Acetonitril, o‐Phenanthrolin, Triphenylphosphinoxid (in Benzol) werden die Verbindungen [V(NO)L4Cl]Cl erhalten. Triphenylphosphinoxid und Pyridin‐N‐oxid reagieren mit [V(NO)3Cl2]n in Chloroform unter Oxydation des Vanadins und Bildung der Oxovanadin(IV)‐Komplexe VOL2Cl2 (L OPPh3, C5H5NO).
Mit den aus a-Aminosaureestern und Chlordiphenylphosphin erhaltenen, optisch aktiven Titelliganden werden eine Reihe von Metallkomplexen von Palladium(II), Platin(II), Rhodium(1) sowie von Chrom-, Molybdan'-, Wolfram-und Mangancarbonylen und deren spektroskopische Daten beschrieben. Die P -N-Bindung in den freien Liganden laljt sich mit HCl spalten, Bis(dipheny1phosphino)glycin-methylester an der CH,-Gruppe monoalkylieren.
Metal Complexes with N,N-Bis(diphenylphosphin0)-a-amino Acid EstersA series of metal complexes of palladium(II), platinum(II), rhodium(1) and carbonyl complexes of chromium, molybdenum, tungsten and manganese with the optically active title ligands (obtained from a-amino acids and chlorodiphenylphosphine) is described. The P -N-bond of the free ligands is cleaved by HCI; bis(dipheny1phosphino)glycine methylester can be monoalkylated at the CH2 group.
Cyclohexyneplatinum (0) complexes Pt(C6H8)L2 [L = PBut2Ph(4), PbutPh2(5)] analogous to the known complex (3) (L=PPh3) have been prepared by reaction of the two-coordinate complexes PtL2 with 1,2-dibromocyclohexene and 1% sodium amalgam. The corresponding tricyclohexylphosphine complex is formed by a similar reaction but it could not be isolated in a pure state. Attempts to prepare analogues of (4) and (5) containing cycloheptyne or cyclooctyne were unsuccessful, possibly because the bulky t-butyl groups of the tertiary phosphines hinder coordination of the larger rings. Bulky tertiary phosphines do not displace PPh3 from (3) but trimethylphosphine reacts with (3) to give successively Pt(C6H8)(PMe3)2(PPh3) (10) and Pt(C6H8)(PMe3)2 (11), as shown by 31P{1H) n.m.r. spectroscopy. The tertiary phosphines in these complexes equilibrate rapidly at room temperature in benzene and only (10) can be isolated as a solid from the reaction. Complexes (4) and (5) react with HCl (1 molar proportion) to give n1-cyclohexen-l-yl complexes trans- PtCl (C6H9)L2 [L= PBut2Ph(6), PButPh2 (7)]. In the absence of air, (4) reacts with methanol at 65°C to give the hydrido complex trans- PtH (C6H9)(PBut2Ph)2 (8). In the presence of oxygen from the air, however, the main product is the dioxygen complex Pt(O2)(Pbut2Ph)2 (9). This represents an unusual example of complete displacement of cyclohexyne from a platinum(0) complex by a π-acceptor ligand.
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