Synthese und Struktur von [Rh₂(μ1‐NO)(μ1‐H)(PiPr₃)₄]: Ein chiraler, NO‐und Hydrid‐verbrückter Rhodium(0)1‐Zweikernkomplex

Abstract

Key Words: Rhodium hydrido complexes 1 Binuclear rhodium complex, molecular structure of 1 NO and hydride as bridging ligands f Axial chirality Synthesis and Structure of [Rhz(p-N0)(pH)(PiPr&]: A Chiral. NOand Hydride-Bridged Binuclear Rhodium(0) Complex The reaction of RhC1, . 3 HzO, PiPr,, iPrONa / iPrOH and N-* Die Position des Hydrido-Liganden wurde mit dem Programm HYDEX berechnet und nicht verfeinert.

Nitrosyl derivatives of the unsaturated dihydrides [Mn2(μ-H)2(CO)6(μ-L2)] (L2 = Ph2PCH2PPh2, (EtO)2POP(OEt)2)

“…Binuclear species having H and NO bridging ligands are exceedingly rare. Actually, the only other binuclear species we can use for comparative purposes is the dirhodium complex [Rh 2 (m-H)(m-NO)(P i Pr 3 ) 4 ] a molecule displaying also a poorly shielded resonance at À7.14 ppm [32].…”

Coordination and Organometallic Chemistry of Metal−NO Complexes

“…The reaction of Rh 2 (OAc) 4 (H 2 O) 2 with KNO 2 and HNO 3 gives Rh 2 (OAc) 4 (NO)(NO 2 ), and Rh(H)(P i Pr 3 ) 3 reacts with Diazald to form Rh(NO)(P i Pr 3 ) 3 , which is unstable and reacts with one molecule of Rh(H)(P i Pr 3 ) 3 to produce the dimer Rh 2 (μ-NO)(μ-H)(P i Pr 3 ) 4 …”

“…1008 The reaction of Rh 2 (OAc) 4 (H 2 O) 2 with KNO 2 and HNO 3 gives Rh 2 (OAc) 4 (NO)(NO 2 ), 1009 and Rh(H)-(P i Pr 3 ) 3 reacts with Diazald to form Rh(NO)(P i Pr 3 ) 3 , which is unstable and reacts with one molecule of Rh(H)(P i Pr 3 ) 3 to produce the dimer Rh 2 (µ-NO)(µ-H)(P i Pr 3 ) 4 . 1010 Two SO 2 molecules in Rh 2 (µ-SO 2 )Cl 2 (µ-dppm) 2 are displaced by 2 equiv of [NO] + to give [Rh 2 (NO) 2 (µ-Cl) 2 (µ-dppm) 2 ] 2+ (vide infra), which contains linear nitrosyl ligands. 1011 The cluster anion [Ir 6 (CO) 11 (µ-CO) 3 (NO)]has been prepared by the one-electron oxidation of [Ir 6 (CO) 15 ] 2-, followed by addition of NO(g).…”