Trans alkenylpyridine and alkenylamine complexes of platinum

Addition of cis-cyclooctene (coe) to K2PtCl4 gives trans-[PtCl2(coe)](2) (1 ), which reacts with excess coe to give trans-PtCl2(coe)(2) (2). Compound 2 was characterized by an X-ray diffraction study and crystals were found to be triclinic, a = 5.7838(5), b = 7.4347(6), c = 9.9972(9) A, alpha = 83.92 4(1), beta = 87.844(2), gamma = 73.546(1), Z = 1, with space group P (1) ov er bar. Addition of 4-vinylpyridine (4vp) to 1 gave trans-PtCl2(4vp)(2) (5) which was also characterized by an X-ray diffraction study. Crystals of 5 were monoclinic, a = 8.2255(6), b = 12.8254(10), c = 6.9624(5) A, beta = 98 .8230(10), Z = 2, with space group P2(1)/c. Although alkenylamines react wi th 1 to give a mixture of products, addition of one equivalent of apve (H2N CH2CH2CH2OCH=CH2) to 1 cleanly afforded the organometallic product trans-Pt Cl2(coe)(thmo) (thmo = tetrahydro-2-methyl-1,3-oxazine) arising from a meta l-catalyzed intramolecular hydroamination of the starting alkenylamine. Ini tial investigations into the functionalization of metal complexes containin g pendant alkene groups have shown that catecholborane can be added in some cases, using a rhodium catalyst, to give the corresponding organoboronate ester platinum compounds.