Verbindungen mit dem 2,4‐Dimethyl‐2,4‐diaza‐1,5‐diphosphapentan‐3‐on‐Grundgerüst; Synthese, Struktur und Eigenschaften von 1,5‐Di‐tert‐butyl‐2,4‐dimethyl‐1,5‐diphenyl‐2,4‐diaza‐l,5‐diphosphapentan‐3‐on und Derivaten

Abstract

N,N-Dimethyl-N-N'-bis(trimethylsily1)urea (1) reacts with tertbutylchlorophenylphosphane (2) to form the monophosphino/ trimethylsilyl-substituted urea 3. Under more vigorous conditions the bisphosphino-substituted derivative 4 was also obtained. The reaction of 4 with the tetracarbonyl norbornadiene derivatives of Cr, Mo, and W furnished the unusual chelate complexes 5 -7 , in which the ligand 4 is coordinated to the metal through one of the two phosphorus atoms and the oxygen atom of the carbonyl group. The free ligand 4 and the isostructural complexes 5 and 6 were subjected to X-ray structure analyses. The approximate twofold symmetry of 4 is lost as a result of a major conformational change on complex formation. In contrast, 4 reacts with Fe2(C0)9 and with (COD)-PtClz (COD = 1,5-cyclooctadiene) to give the complexes 8 and 9. In both 8 and 9 the ligand 4 is coordinated by both phosphorus atoms. Reaction of 4 with sulfur and selenium led to -C7H8' I I .. M = Cr,Mo,W C7Hg = Norbornadien 5:M:Cr 6: M = M o 7 : M = W Chem. Ber. 124 (1991) 2705-2714

{N-[tert-Butyl(phenyl)phosphino]-N′-diphenylphosphino-N,N′-dimethylurea-P,P′}dichloroplatinum(II) chloroform solvate

“…1. The structure determination confirms the expected P,P′-bonding mode of the ligand; related derivatives of pentacarbonylchromium and -molybdenum unexpectedly proved to be P,O-bonded (Vogt et al, 1991). The geometry at platinum is square planar; the Pt-Cl bond lengths are exactly equal, but the Pt-P bond to the Ph 2 P moiety is slightly shorter than that to t Bu(Ph)P ( Table 1).…”

“…The title compound was prepared by treating (cyclooctadiene)PtCl 2 with the phosphinourea ligand in dichloromethane (Vogt, 1992). Single crystals were obtained by evaporation from chloroform.…”

“…The authors thank Mr A. Weinkauf for technical assistance. The title compound, (I), formed part of a study of phosphorus-substituted N,N′-diorganylureas (Vogt, 1992). It crystallizes as a chloroform monosolvate.…”

A hydroxyaminophosphane derived from 2-imidazolidone and its unusual structure in solution

“…The 31 P-{ 1 H}-NMR spectrum shows a single signal at δ = 34.2 and thus in the same region as the known compound (Ph 2 PNH) 2 CO, but significantly shifted upfield compared to the dimethyl urea derivatives [4]. The signal for the carbonyl carbon atom in the 13 C{ 1 H}-NMR (δ = 163.6, t, 2 J PC = 22.5 Hz) and the IR-spectrum (1702 cm -1 , st) are as expected.…”

“…Recently, interest in phosphino urea derivatives as ligands for transition metals has increased [1][2][3][4][5]. The main focus is on the acyclic representatives and therefore the derivatives of urea itself.…”