Crystal structures of two PCN pincer iridium complexes and one PCP pincer carbodi-phospho-rane iridium inter-mediate: substitution of one phosphine moiety of a carbodi-phospho-rane by an organic azide

• Published in: Acta crystallographica. Section E, Crystallographic communications Vol. 75; no. Pt 1; pp. 75 - 80
• Main Authors: Partl, Gabriel Julian, Nussbaumer, Felix, Schuh, Walter, Kopacka, Holger, Wurst, Klaus, Peringer, Paul
• Format: Journal Article
• Language: English
• Published: England International Union of Crystallography 01-01-2019
• Subjects: Research Communications; iridium; non-innocent behaviour; PCP pincer; organic azide; crystal structure; PCN pincer; reductive elimination; carbodi­phospho­rane
• ISSN: 2056-9890; 2056-9890
• DOI: 10.1107/S2056989018017644

The structure of [Ir{(4-Cl-C
H
N
)C(dppm)-κ
,
,
}(dppm-κ
,
')]Cl·1.5CH
Cl
·0.5C
H
(C
H
Cl
IrN
P
·1.5CH
Cl
·0.5C
H
) (
), dppm = bis-(di-phenyl-phosphino)methane {systematic name: [7-(4-chloro-phen-yl)-1,1,3,3-tetra-phenyl-5,6,7-tri-aza-κ
-1,3λ
-diphospha-κ
-hepta-4,6-dien-4-yl][methyl-ene-bis(di-phenyl-phosphine)-κ
,
']iridium(I) chloride-di-chloro-methane-toluene (2/3/1)}, resulting from the reaction of [IrClH{C(dppm)
-κ
,
,
)(MeCN)]Cl (
) with 1-azido-4-chloro-benzene, shows a monocationic five-coordinate Ir
complex with a distorted trigonal-bipyramidal geometry. In
, the iridium centre is coordinated by the neutral triazeneyl-idene-phospho-rane (4-Cl-C
H
N
)C(dppm) acting as a PCN pincer ligand, and a chelating dppm unit. The structure of the coordination compound [IrCl(CN)H(C(dppm)
-κ
,
,
)]·CH
CN, (C
H
ClIrNP
·CH
CN) (
) [systematic name: chlorido-cyanidohydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,3λ
,5λ
,7-tetra-phospha-κ
,
-hept-3-en-4-yl)iridium(III) aceto-nitrile monosolvate], prepared from
and KCN, reveals an octa-hedral Ir
central atom with a meridional PCP pincer carbodi-phospho-rane (CDP) ligand; the chloride ligand is located
to the central carbon of the CDP functionality while the hydrido and cyanido ligands are situated
to each other. The chiral coordination compound [Ir(CN)((4-Cl-C
H
N
)CH(CH(P(Ph)
)
)-κ
,
,
)(dppm-κ
,
')]·2CH
OH, (C
H
ClIrN
P
·2CH
OH) (
) (systematic name: {4-[3-(4-chloro-phen-yl)triazenido-κ
]-1,1,3,3-tetra-phenyl-1,3λ
-diphospha-κ
-but-2-en-4-yl}cyanido[methyl-enebis(di-phenyl-phosphine)-κ
,
']iridium(III) methanol disolvate), formed via prolonged reaction of 1-azido-4-chloro-benzene with
, features a six-coordinate Ir
central atom. The iridium centre is coordinated by the dianionic
PCN pincer ligand [(4-Cl-C
H
N
)CH(CH(P(Ph
)
)
)], a cyanido ligand
to the central carbon of the PCN pincer ligand and a chelating dppm unit. Complex
exhibits a 2:1 positional disorder of the Cl
anion. The CH
Cl
and C
H
solvent mol-ecules show occupational disorder, with the toluene mol-ecule exhibiting additional 1:1 positional disorder with some nearly overlying carbon atoms.