Abstract
The structure of [IrCl2(C58H51N3P4)]Cl·5.5CH3CN or [IrCl2(NHCHPh)(((dppm)C(N2dppm))-κ 3P,C,P)]Cl·5.5CH3CN [3, dppm = bis-(di-phenyl-phos-phino)methane; systematic name: di-chlorido(1,1,3,3,7,7,9,9-octa-phenyl-4,5-di-aza-1,3λ5,7λ4,9-tetra-phosphanona-3,5-dien-6-yl-κ2 P 1,P 9)-(phenyl-methanimine-κN)iridium(III) chloride aceto-nitrile hemihendeca-solvate], resulting from an oxygen-mediated cleavage of a triazeneyl-idene-phospho-rane ligand producing a diazo-methyl-ene-phospho-rane and a nitrene moiety, which in turn rearrange via a Staudinger reaction and a 1,2-hydride shift to the first title complex, involves a six-coordinate IrIII complex cation coordinated by a facial PCP pincer ligand, a benzaldimine and two chlorido ligands. The pincer system features a five- and a seven-membered ring, with the central divalent carbon of the PCP pincer ligand being connected to a phosphine and a diazo-phospho-rane. The chlorido ligands are positioned trans to the central carbon atom and to the phospho-rus donor of the seven-membered ring of the pincer system, respectively. A chloride ion serves as counter-ion for the monocationic complex. The structure of [IrI(C26H22N2P2)(C26H22P2)(C6H7N)]I(I3)·0.5I2·CH3OH·0.5CH2Cl2 or [IrI(NHCHPh)((dppm)C(N2)-κ 2P,C)(dppm-κ 2P,P')]I(I3)·0.5I2·CH3OH·0.5CH2Cl2 {4, systematic name: (4-diazo-1,1,3,3,-tetra-phenyl-1,3λ4-diphosphabutan-4-yl-κP 1)iodido[methyl-enebis(di-phenyl-phosphine)-κ2 P,P'](phenyl-methanimine-κN)iridium(III) iodide-triiodide-di-chloro-methane-iodine-methanol (2/2/1/1/2)}, accessed via treatment of the triazeneyl-idene-phospho-rane complex [Ir((BnN3)C(dppm)-κ 3P,C,N)(dppm-κ 2P,P')]Cl with hydro-iodic acid, consists of a dicationic six-coordinate IrIII complex, coordinated by a bidentate diazo-methyl-ene-phospho-rane, a benzaldimine, a chelating dppm moiety and an iodido ligand. The phospho-rus atoms of the chelating dppm are trans to the central carbon atom of the diazo-methyl-ene-phospho-rane and the iodide ligand, respectively. Both an iodide and a triiodide moiety function as counter-ions. The aceto-nitrile solvent mol-ecules in 3 are severely disordered in position and occupation. In 4, the I3 - anion is positionally disordered (ratio roughly 1:1), as is the I- anion with a ratio of 9:1. The di-chloro-methane solvent mol-ecule lies near a twofold rotation axis (disorder) and was refined with an occupancy of 0.5. Another disorder occurs for the solvent methanol with a 1:1 ratio.
Highlights
The structure of [IrCl2(C58H51N3P4)]ClÁ5.5CH3CN or [IrCl2(NHCHPh)(((dppm)C(N2dppm))-3P,C,P)]ClÁ5.5CH3CN [3, dppm = bis(diphenylphosphino)methane; systematic name: dichlorido(1,1,3,3,7,7,9,9-octaphenyl-4,5-diaza-1,35,74,9-tetraphosphanona-3,5-dien-6-yl-2P1,P9)(phenylmethanimineN)iridium(III) chloride acetonitrile hemihendecasolvate], resulting from an oxygen-mediated cleavage of a triazeneylidenephosphorane ligand producing a diazomethylenephosphorane and a nitrene moiety, which in turn rearrange via a Staudinger reaction and a 1,2-hydride shift to the first title complex, involves a six-coordinate IrIII complex cation coordinated by a facial PCP pincer ligand, a benzaldimine and two chlorido ligands
The pincer system features a five- and a seven-membered ring, with the central divalent carbon of the PCP pincer ligand being connected to a phosphine and a diazophosphorane
We describe the fragmentation of a triazene into diazo and nitrene parts in the coordination sphere of iridium
Summary
The structure of 3 (Fig. 1) shows a six-coordinate monocationic IrIII complex and one chloride counter-ion. Examination of the C4—N3 bond length within the benzaldimine ligand [1.270 (6) A ] indicates a double bond and is almost identical to that observed in compound 4 [1.267 (8) A ] and a previously reported iridium benzaldimine complex [1.260 (6) A ] involving a phosphorus donor atom trans to the benzaldimine nitrogen donor (Albertin et al, 2008). The environment around the ylidic carbon C1 is trigonal planar, with the bond angle N3—C1—P2 exhibiting the largest deviation from a regular symmetry [114.8 (5)] Both the N3— N2 [1.095 (9) A ] and the N3—C1 [1.305 (9) A ] bond lengths are slightly shorter, compared to the corresponding mean values of ten previously reported structures of diazo compounds [1.121 and 1.323 A , respectively; Cambridge Structural Database (Groom et al, 2016)].
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