Structure of tris(diphenylphosphino)amine

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

“…The latter was obtained in low yield by treatment of DPPA with n -BuLi (1 equiv), followed by addition of an equimolar amount of PPh 2 Cl, and exhibited a 31 P NMR singlet resonance at δ 59.2 ppm. The solid-state structure of ligand 141 was confirmed by XRD a few years later, the characteristic structural parameters of which are reported in Table , and the authors highlighted a (quasi-)­planar NP 3 fragment, as earlier discovered for N­(PF 2 ) 3 by electron diffraction in the gas phase . Although 141 was obtained in low yield, it remains an important finding, since previous attempts to synthesize it led instead to the isolation of its formula isomer [(C 6 H 5 ) 2 P–P­(C 6 H 5 ) 2 N–P–(C 6 H 5 ) 2 ] …”

“…Biricik and colleagues studied the coordination chemistry, toward d 8 and d 10 metal centers, of a series of new N-aryl-(bis-ether)-functionalized DPPA-type ligands of general formula (Ph 2 P) 2 N−C 6 H 3 −R [R = 3,5-OMe (75), 2,5-OMe (76), 2,4-OMe (77), 3,4-OMe (78)] prepared via the classical aminolysis of the respective commercially available dimethoxyanilines (Scheme 18). 66 The significant difference in chemical shifts observed in the 31 P NMR spectra of the free ligand [68.6 ppm (75), 64.7 ppm (76), 66.1 ppm (77), and 71.1 ppm (78)] illustrates the influence of the substituents position in such N-functionalized DPPA-type ligands (Table 7). An equimolar reaction between ligands 75−78 and [MCl 2 (COD)] (M = Pt, Pd) afforded the corresponding platinum and palladium cis-dichloride complexes 79−82 and 83−86, respectively (Scheme 18).…”

“…77 The latter was obtained in low yield by treatment of DPPA with n-BuLi (1 equiv), followed by addition of an equimolar amount of PPh 2 Cl, and exhibited a 31 P NMR singlet resonance at δ 59.2 ppm. The solid-state structure of ligand 141 was confirmed by XRD a few years later, the characteristic structural parameters of which are reported in Table 12, 78 and the authors highlighted a (quasi-)planar NP 3 fragment, as earlier discovered for N(PF 2 ) 3 by electron diffraction in the gas phase. 79 76 The pattern of the 31 P NMR spectrum of the Mo(0) species 143 corresponded to an A 2 X spin system, with one doublet centered at 102.9 ppm for the two equivalent P atoms coordinated to the metal center (PNP chelate moiety), coupled ( 2 J P,P = 22 Hz) to the free phosphorus donor, which appeared as a triplet at 76.0 ppm, similarly to the situation in the Cr analog 142 (Table 12).…”

The Molecular Structure of Tris(dimethylstibino)amine

“…W ith the heavier group V elem ents, planar structures have been found only for (P h 2P )3N [6] and a few m ore com plicated p h osphinoam ines [8], but very little is know n ab o u t the configuration of related com pounds with arsenic [7], Tris(stibino)-am ines never have been structurally characterized. We have th erefo re d eterm in ed the crystal struc ture of tris(dim ethylstibino)am ine N (S bM e2)3, w hen this com pound becam e available to us in sin gle crystal form from reactions u n d ertak en (w ith out success) for th e synthesis of poly(stibino)alkanes (E xperim ental Part).…”

Bildung und Struktur von Tris(diphenylstibino)amin/Formation and Structure of Tris(diphenylstibino)amine

“…Die Kri stallstruktur dieses Amins besteht aus unabhängi gen (Me2Sb)3N Molekülen mit streng trigonal-planarem Sb3N Gerüst [2]. Diese Konfiguration am Stickstoff ist für tertiäre Amine ungewöhnlich; sie tritt jedoch häufiger bei Tris(organoelement)aminen wie (H3E)3N (E = Si [3], Ge [4], Sn [5]), (Ph2P)3N [6] oder (Me2 As)3N [7] auf. Auch bei dem zu (Me2Sb)3N isoelektronischen Oxoniumbromid, (Me2Sb)30 +Br~ [8] (4) Sb (3) .…”