Platinum Complexes with Carbonyl, Isocyanide, and Carbene Ligands

Rourke, Jonathan P.

doi:10.1016/b0-08-045047-4/00105-9

Cited by 8 publications

(4 citation statements)

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“…Isonitriles, RNC, are versatile reagents in organic and organometallic chemistry, and their transformations allow the synthesis of a wide range of important products . Besides the application of uncomplexed isonitriles for the stereoselective synthesis of bis-amides, heterocycles, and peptides via the so-called multicomponent reactions, − RNC species also attract attention in coordination chemistry due to their ability to form a diversity of types of complexes including aminocarbynes , and heteroatom-stabilized metallacarbenes , (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

“…Two general routes for the preparation of heteroatom-stabilized metallacarbenes are commonly utilized, viz., the coordination of preprepared free carbenes to a metal center, and the transformation of the metal-bound isonitrile upon nucleophilic attack (Scheme ). The former method is limited mostly to imidazol-2-ylidene, 1,2,4-triazole-3-ylidene, and 1,3-thiazol-2-ylidene derivatives with bulky substituents (some noncyclic species are also known) due to an insufficient stability of the uncomplexed carbenes, while the limitation of the latter route is the relatively low electrophilic activation of the isonitriles. However, the metal-mediated approach appears to be more versatile than the route associated with the direct complexation due to the wide range of available nucleophiles and isonitriles, thus providing a great variety of (carbene)[M] species.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Reactions of complexed isonitriles with nucleophiles have been repeatedly reviewed , (including a survey by one of us), showing that the vast majority of the reported examples are based on the addition of nucleophiles with sp 3 -N or O donor centers, viz. amines and alcohols. , In this context, additions of sp 3 -N nucleophiles, viz. ammonia or primary or secondary amines, to metal-bound RNC molecules are well documented, and this interaction brings about formation of the amino-carbene C(NRR′′)N(H)R ligands …”

Section: Introductionmentioning

confidence: 99%

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Coupling between 3-Iminoisoindolin-1-ones and Complexed Isonitriles as a Metal-Mediated Route to a Novel Type of Palladium and Platinum Iminocarbene Species

et al. 2008

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The reaction between isonitrile in cis-[MCl2(CNR)2] [M = Pd, R = Cy 1, Bu t 2, C6H3(2,6-Me2) 3; M = Pt, R = Cy 4, Bu t 5, C6H3(2,6-Me2) 6] and various unsubstituted or substituted iminoisoindolin-1-ones HNCC6R1R2R3R4CONH [R1−R4 = H 7; R1, R3, R4 = H, R2 = Me/R1, R2, R4 = H, R3 = Me 8 (isomeric mixture); R1, R4 = H, R2, R3 = Cl 9] proceeds under reflux conditions in CHCl3 for 2 h. The subsequent workup provides complexes [MCl{C(NC(C6R1R2R3R4CON))N(H)R}(CNR)] (M = Pd, 10−18; M = Pt, 19−27), bearing a novel type of carbene ligands, which were isolated in good (80−85% for the PdII complexes) to moderate (60−65% for the PtII species) yields. The addition of the iminoisoindolin-1-one to isonitriles is metal-mediated and has a general character. The reaction of cis-[PtCl2(CNC6H4OMe-4)2] (28) with 7 affords a mixture of PtII-containing species including the monoadduct [PtCl{C(NC(C6H4CON))N(H)C6H4OMe-4}(CNC6H4OMe-4)] (29), the unusual binuclear compound [Pt2{C(NC(C6H4CON))N(H)C6H4OMe-4}2(CNC6H4OMe-4)2(μ-HNCC6H4CON)](Cl) (30) with a bridging monodeprotonated 3-iminoisoindolin-1-one, and [Pt(C6H4CONCNH){C(NC(C6H4CON))N(H)C6H4OMe-4}(CNC6H4OMe-4)] (31), the latter resulting from the replacement of the chloro ligand in 29 by the deprotonated iminoisoindolin-1-one. Complexes 10−27 were characterized by elemental analyses (C, H, N), ESI+-MS, IR, and 1D (1H, 13C{1H}) and 2D (1H,1H-COSY, 1H,13C-HMQC/1H,13C-HSQC, 1H,13C-HMBC) NMR spectroscopies, while 29−31 by ESI+-MS, IR, and 1H NMR. In addition, the structures of three carbene complexes (10, 27, and 30) were elucidated by single-crystal X-ray diffraction analysis.

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