ChemInform Abstract: APPLICATION OF (13)C NMR TO THE DETERMINATION OF METAL‐CARBON SIGMA BOND FORMATION IN CYCLOMETALLATION REACTIONS WITH NITROGEN DONOR LIGANDS

Garber, A. R.; Garrou, Philip E.; Hartwell, George E.; Smas, M. J.; Wilkinson, James A.; Todd, Lord

doi:10.1002/chin.197522086

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“…Introducing metal into C-H bond have been observed in many compounds like quinoline and Schiff base substrates [19]. A significant amount of work has been done on the heterocyclic aromatic species, 8-substituted quinoline [20][21][22][23][24] and 2-(benzylidenamino) pyridines [25][26][27][28][29]. Coordination of the metal with nitrogen atom in aryl amines results in a favorable geometry for introducing of the metal into neighboring C-H or C-C bond [21,25,26,30].…”

Section: Resultsmentioning

confidence: 99%

Hydridothiazole Rhodium Complexes as a Result of C-H Bond Activation in Iminothiazoles Chelating Ligands

Al-hamidi¹,

Alsaygh²,

Al‐Najjar³

2014

CHEM

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A series of 20 Schiff base ligands derived from 2-aminothiazole and its derivatives and aryl aldehydes with either [RhCl(PPh3)3] or [Rh(µ-Cl)(COD)]2 in the presence of 4 equivalents of PPh3 lead to an Rh(III) cyclometallated complex and the imine ligand (C-H) bond has been added to the metal (C-M-H). The complexes were investigated by using I.R., 1H, 13C and 31P NMR Spectroscopic techniques. The signal of the (C-H) ligand was observed as trans to the nitrogen atom in the complex which is a donor ligand. Graphical Abstract: Total synthesis of hydridothiazole rhodium complexes possessing rhodium hydride signal at δ (-14.60 to-15.04) ppm, trans to N-donor ligand and iminoyl carbon (7C=N) signal in Rh (III) observed at δ (220.1-237.6)ppm, lower field and suggestive of carbine like properties.

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