Syntheses and crystal structures of [IrIII{C(CHCO2Et)(dppm)2-κ4 P,C,C',P'}ClH]Cl·2.75CH2Cl2 and its derivatives, [IrIII{C(CHCO2Et)(dppm)2-κ4 P,C,C',P'}(CH2CO2Et)Cl]Cl·CH3OH·0.5H2O, [IrIII{C(CHCO2Et)(dppm)2-κ4 P,C,C',P'}Cl2]Cl·CH3OH·2H2O and [IrIII{C(CHCO2Et)(dppm)2-κ4 P,C,C',P'}(CH2CO2Et)(CO)]Cl2·2CH2Cl2·1.5H2O.

Inge Schlapp-Hackl,Paul Peringer,Klaus Wurst,Christoph Falschlunger,Walter Schuh,Holger Kopacka,Kathrin Zauner

doi:10.1107/s2056989018017024

Inge Schlapp-Hackl, Paul Peringer + Show 5 more

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https://doi.org/10.1107/s2056989018017024

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Abstract

The common feature of the four iridium(III) salt complexes, (bis-{[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methane-κ4 P,C,C',P')chlorido-hydridoiridium(III) chloride methyl-ene chloride 2.75-solvate (4), (bis-{[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methane-κ4 P,C,C',P')chlorido-(eth-oxy-oxoethanido)iridium(III) chloride-methanol-water (1/1/0.5) (5), (bis-{[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methane-κ4 P,C,C',P')di-chlorido-iridium(III) chloride-methanol-water (1/1/2) (6) and (bis-{[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methane-κ4 P,C,C',P')carbon-yl(eth-oxy-oxoethanide)iridium(III) dichloride-meth-yl-ene chloride-water (1/2/1.5) (7) or in terms of their formulae [Ir(C55H50O2P4)ClH]Cl·2.75CH2Cl2 (4), [Ir(C4H7O2)(C55H50O2P4)Cl]Cl·CH3OH·0.5H2O (5), [Ir(C55H50O2P4)Cl2]Cl·CH3OH·2H2O (6) and [Ir(C4H7O2)(C55H50O2P4)(CO)]Cl2·2CH2Cl2·1.5H2O (7) is a central IrIII atom coordin-ated in a distorted octa-hedral fashion by a PCCP ligand system and two additional residues, such as chlorides, a hydride, a carbonyl or an alkyl unit. Thereby, the PCP pincer ligand system and the residue trans to the carbodi-phospho-rane (CDP) C atom surround the iridium(III) transition metal in the equatorial plane under the formation of two five-membered dissimilar chelate rings [C-CCDP-P (4, 5, 6 and 7) for the first ring: 120.2 (3), 121.9 (5), 111.2 (3) and 121.7 (2) °; for the second ring: 112.1 (3), 113.5 (5), 120.5 (3) and 108.3 (2)°]. A cyclo-propane-like heterocycle is positioned approximately orthogonal (84.21-88.85°) to the equatorial plane, including an alkyl-idene bridge connecting the IrIII atom and the coordinating CDP atom of the PCP subunit. In general, the neutral PCCP ligand system coordinates the metal in a tetra-dentate way via three Lewis acid/base bonds and by an alkyl-idene unit presenting strengthened inter-actions. In all the crystal structures, (disordered) solvent mol-ecules are present in the voids of the packed mol-ecules that inter-act with the positively charged complex and its chloride counter-ion(s) through weak hydrogen bonding.

Highlights

Carbodiphosphoranes (CDP) in combination with transition metals initialize a huge variety of functionalities
An electrophilic reaction partner such as a transition metal establishes a nucleophilic attack of the diazo subunit and, according to the choice of the reaction conditions, the elimination of the nitrogen leaving group is supported
The reaction of a diazo compound with an electrophilic and a nucleophilic reaction partner initiates a mechanism that can be described as a cheletropic-like process

Summary

DÁ Á ÁA

In the structure of 4, there are weak C—HÁ Á ÁCl interactions between the chloride counter-ion and the methylene groups of the PCP pincer ligand system [Cl2Á Á ÁH2B = 2.58 A , H3BÁ Á ÁCl2(x À 1, y, z) = 2.83 A ] exhibiting distances shorter than the sum of the van der Waals radii (Table 2, Fig. 6). Such C—HÁ Á ÁX interactions are a common feature of complexes containing dppm or related ligands (Jones & Ahrens, 1998).

Crystal data Chemical formula

Nonius KappaCCD diffractometer

Findings

Special details