Abstract:
The cage-phosphine 2-thia-1,3,5-triaza-7-phosphaadamantane-2,2-dioxide (PASO(2)) was reacted with various transition metal precursors to give the complexes cis-[Mo(CO)(4)(PASO(2))(2)], [AuCl(PASO(2))] cis-[PtCl(2)(PASO(2))(2)], [Ru(eta(6)-p-cym)Cl(2)(PASO(2))], [Rh(eta(5)-C(5)Me(5))Cl(2)(PASO(2))], and [Rh(eta(5)-C(5)Me(5))Cl(PASO(2))(2)](+) as well as the cyclometalated palladium(II) complexes [PdCl{kappa C,N-C(6)H(4)C(Ph)NCH(2)CO(2)Et}(PASO(2))] and [PdCl(kappa C,N-1,8-C(10)H(6)NMe(2))(PASO(2))]. The compounds were characterized by spectroscopic methods and several examples by single-crystal X-ray diffraction. The stereoelectronic properties of PASO(2) were determined by computational methods and were compared with those of other phosphines, in particular 1,3,5-triaza-7-phosphaadamantane.