<i>ortho</i>‐Metalated Dinuclear Rhodium(II) Compounds. Synthesis, Structure and Catalytic Applications

Lahuerta, Pascual; Estevan, Francisco

doi:10.1002/9783527618316.ch2c

Cited by 3 publications

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“…As shown in Figure , the ligand [2-C 6 H 4 PPh 2 ] − usually binds as a chelate group (κ 2 P,C ), forming a four-membered ring, but the bridging (μ 2 P,C ) mode is also well established, for example, in complexes of digold(I), − diplatinum(I), , tetrapalladium(II), , and dirhodium(II). − Facile interconversion between these coordination modes has been demonstrated, especially in the case of palladium(II). , …”

Section: Introductionmentioning

confidence: 99%

A Triad of Bis(orthometalated) d⁸-Complexes Containing Four-Membered Rings

et al. 2008

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Reaction of 2-LiC6F4PPh2 with [MCl2(SEt2)2] in diethyl ether gives the monomeric bis(chelate) complexes trans-[M(κ2-2-C6F4PPh2)2] [M = Pt (1), Pd (2)] or, in the case of platinum, a mixture of cis- and trans-isomers. Treatment of a mixture of NiCl2 and 2-BrC6F4PPh2 in THF with zinc dust gives trans-[Ni(κ2-2-C6F4PPh2)2] (3). The four-membered chelate rings in 1−3 are opened on addition of the bidentate ligand 1,2-bis(diphenylphosphino)ethane (dppe), and, in the case of 3, 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen), to give complexes of the type cis-[M(κC-C6F4-2-PPh2)2(L-L)] [L-L = dppe, M = Ni (6), Pd (7), Pt (8); M = Ni, L-L = bipy (9), phen (10)], in which the PPh2 groups are uncoordinated. Complexes 6−8 show unexpectedly large four-bond coupling constants (4 J PF), in the range 75−95 Hz, between the fluorine atoms (F6) ortho to the metal−carbon σ-bond and the phosphorus atoms of the PPh2 groups, possibly because F6 and the lone pairs on phosphorus adopt a close to synperiplanar conformation. Treatment of 2 with [PdCl2(NCMe)2] gives the dinuclear complex [Pd2(μ-Cl)2(κ2-2-C6F4PPh2)2] (11), which dimerizes in solution to the tetranuclear complex [Pd4(μ-Cl)4(μ-2-C6F4PPh2)4] (12) as a result of opening of the chelate 2-C6F4PPh2 rings. Carbon monoxide inserts into a nickel−carbon σ-bond of 3 to give, after oxidation, bis-2,2′-(diphenylphosphinoyl)octafluorobenzophenone, {2,2′-C6F4P(O)Ph2}2CO (14). The molecular structures of complexes 1−3, 6, 8, 9, and 14 have been determined by single-crystal X-ray methods.

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