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Neopentyl and Trimethylsilylmethyl Compounds of Rhodium(III) and Iridium(III) with ortho-Metallated Triphenylphosphine. X-Ray Crystal Structure of

DOI: 10.1039/DT9860000803

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 803 - 812 (1986)

Update date:2022-07-30

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Authors:

Andreucci, LucaAndreucci, Luca

Diversi, PietroDiversi, Pietro

Ingrosso, GiovanniIngrosso, Giovanni

Lucherini, AntonioLucherini, Antonio

Marchetti, FabioMarchetti, Fabio

et al.et al.

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Article abstract of DOI:10.1039/DT9860000803

The compound 5-C5Me5)(PPh3)> reacts with Li(CH2SiMe3) to give the ortho-metallated complex (2), and with Mg(CH2SiMe3)Cl in CH2Cl2 (molar ratio 1:1) to yield 5-C5Me5)(PPh3)>, (3).Complex (3) is converted by the action of Li(CH2SiMe3) into the ortho-metallated compound (2).The reaction of 5-C5Me5)(PPh3)> with Mg(CH2SiMe3)Cl in CH2Cl2 gives , (6), and 5-C5Me5)(PPh3)>.Reaction of 5-C5Me5)(PPh3)> with Mg(CH2CMe3)Cl or Li(CH2CMe3) in diethyl ether affords a mixture of , , and 5-C5Me5)(C2H4)(PPh3)>, while reaction in CH2Cl2 in equimolar amounts gives 5-C5Me5)(PPh3)>.Reaction of 5-C5Me5)(PPh3)> with Mg(CH2CMe3) gives .The X-ray crystal structure analysis of compound (6) has been carried out: a=17.537(7), b=11.304(4), c=15.410(7) Angstroem, β=94.49(1) deg, space group P21/n, Z=4, R=0.0361 for 4114 observed reflections.The 'piano-stool' metal co-ordination polyhedron is deformed by ortho-matallation which imposes a 67.0(2) deg angle at iridium in the matallacycle, while the other angles, P-Ir-C(17) 89.0(2) and C(17)-Ir-C(36) 89.2(2) deg, between the 'legs' of the 'stool' are near to 90 deg.The bulky C5Me5 ligand (effective cone angle 146 deg), in approaching the metal, produces large widenings of the other co-ordination polyhedron angles: Cp-Ir-P 137.0(3), Cp-Ir-C(36)(benzene) 133.4(3) deg, and Cp-Ir-C(17)(silyl) 122.6(3) deg (Cp=centroid of C5Me5).The ortho-metallated ring is nearly planar, (P-Ir-C)<*>(P-C-C) 5.3(3) deg, and bent by only 6.6(2) deg with respect to the metal-bound benzene ring which maintains its planarity; the only deformation this ring suffers involves the endocyclic angles at the carbon bound to phosphorus which widen to 124.5(5) deg and at the ortho-carbons which narrow to 115.9(6) and 116.7(5) deg.

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Product name:chloro(η5-pentamethylcyclopentadienyl)(trimethylsilylmethyl)(triphenylphosphine)rhodium(III)

Cas No:104731-05-7

104731-05-7

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