Elementorganische Amin/Imin‐Verbindungen, XXIX ¹⁾ [(OC) ₄ Re−NR− P(Cl)(NR ₂ )−NR], R = SiMe ₃ , ein vielseitiger Synthesebaustein

Abstract

Die Cothermolyse von [(OC)dRk-NR-P(Cl)(NR2)-AR] (1) und RR'N-P=NR (2a: R = R = %Mes, 2b R = SiM+ R' = tBu) ergibt bei 2s neben dem Spirocyclus [RN-SiMe2-CH2 -(OC),Re -P-NR' -P(NR)(NHR) -kR'] (3a,b) den tricvclischen KomDIex 4. Die Substitution von 1 rnit LiCH2-SiMe3 (5) fiihrt zum fiinffach koordinierten d6-Rheniumkomplex [(OC)~R~-NR-P(CHIRXNR~)-~~R] (6), der mit (MeO),P Kohlenmonoxid-Substitution, mit f BuNC zusiitzlich Addition ergibt. 3b, 4 und 6 wurden durch Rontgenstrukturanalysen charak terisiert. Bei der Thermolyse von [(OC),Rk -NR -P(Cl)(NR,)-NR] (l), R = SiMe3, entstehen neben einer tricyclischen Phosphor-Dispiro-Rheniumverbindung der cubanartige Rheniumkomplex [Re2(CO)6(p3-NR)4(p3-PNR)z] sowie ein tetracyclischer Phosphor-Stickstoff-Rheniumkomplex'). P -Cl-Substitutionsreaktionen bei 1 a) Cothermolyse mit Amino(imino)phosphanen 1 und die Amino(imin0)phosphane 2 ergeben bei deren Cothermolyse die polycyclischen Phosphor-Stickstoff-Rheniumkomplexe 3 und 4.

Lithiation of Tris(alkyl- and arylamido)orthophosphates EP[N(H)R]3 (E = O, S, Se): Imido Substituent Effects and PE Bond Cleavage

“…This observation can be attributed to the formation of the bis-spirocyclic complex 9 ‘ in solution at 23 °C through coordination of a second THF molecule to the Li + ions (Scheme ). This type of ring-opening has been observed in structurally related rhenium complexes in which the ligands are CO instead of THF molecules . At −50 °C, the resonances at δ 1.28 and 1.53 are still predominant, but new resonances at δ 1.24, 1.27, and 1.49 (1:1:1), attributable to 9 , are evident.…”

“…This type of ring-opening has been observed in structurally related rhenium complexes in which the ligands are CO instead of THF molecules. 41 At -50 °C, the resonances at δ 1.28 and 1.53 are still predominant, but new resonances at δ 1.24, 1.27, and 1.49 (1:1:1), attributable to 9, are evident. At -100 °C, the latter resonances dominate over those of 9′.…”

Syntheses and crystal structures of mono- and bi-metallic zinc compounds of symmetrically- and asymmetrically-substituted bis(amino)cyclodiphosph(V)azanes

“…The coordination modes N and O are hybrids of facial-and lateral-coordinations, and each has been observed only once thus far. Highly sterically-encumbered metal moieties, i.e., metals bearing additional Chart 4. ligands, seem to prefer the more open lateral coordination sites (K) because of excessive steric crowding above the (PN) 2 ring, while M has only been observed in cases where the ligand was formed in situ [38,39].…”

“…The by far most common coordination mode is the bilateral one (K), with the bifacial (L) and the heterocubic (M) modes being the next most common. Based on the data from previous studies by Chivers [6,[9][10][11], Scherer [39] and N€ oth [7], it appears that bis(amido)cyclodiphosph(V)azanes coordinate two metals laterally (K) as long as the covalent radius of the metal is less than about 1.28 A. Thus aluminum has shown exclusively lateral coordination, but metal atoms with larger covalent radii (Na, K) prefer the sterically more accessible positions above and below the (PN) 2 ring (L).…”

Titanium complexes of bis(1°-amido)cyclodiphosph(III)azanes and bis(1°-amido)cyclodiphosph(V)azanes: facial versus lateral coordination †

“…Scherer et al had discovered that Re(CO) 5 Cl reacts with [(Me 3 Si) 2 NP(᎐ ᎐ NSiMe 3 ) 2 ], Scheme 5, to yield three products, of which only two (11 and 12) are pertinent to our results. 18 In 11 the bis(amido)cyclodiphosph-()azane chelates two Re(CO) 4 fragments as a bisphosphoranate to form a trispirocyclic complex, quite similar to 5 and 6. Compound 12, by contrast, is a heterocubic bimetallic bis(amido) complex, which is structurally related to 2.…”