SYNTHESES AND STRUCTURES OF THE 5-COORDINATE COMPLEXES [M(N-N)([9]ANES(3))](PF6)(2) (M=PD, (N-N)=2,2'-BIPYRIDINE M=PT, (N-N)=1,10-PHENANTHROLINE ([9]ANES(3))=1,4,7-TRITHIACYCLONONANE)

Syntheses and crystal structure determinations of [Pb(bpy)[9]aneS(3))] [PF6](2) (bpy = 2,2'-bipyridine; [9]aneS(3) = 1,4,7-trithiacyclononane ) and [pt(phen)([9]aneS(3))][PF6](2) (phen = 1, 10-phenanthroline) are reported. The Pd compound (C16H20N2S3PdP2F12) crystallizes in triclin ic space group P1 Nno. 2), with a = 10,376(3) Angstrom, b = 10.810(2) Angstrom, c = 10.907(2) Angstrom, alpha = 84.25(1)degrees, beta = 87.2 5(2)degrees, gamma = 84.89(2)degrees, D-c = 2.009 g cm(-3), and Z = 2; the Pt compound (C18H20N2S3PtP2F12) crystallizes in orthorhombic spac e group Pbca (No. 61), with a = 15.422(3) Angstrom, B = 10.617(2) Angs trom, c = 31.335(6) Angstrom, D-c = 2.189 g cm(-3), and Z = 8. Each st ructure features a five-coordinate metal center in a distorted square- pyramidal geometry. Two diimine nitrogens and two of the S-donors of [ 9]-aneS3 are bound in the square plane, (M-N 2.06-2.07 Angstrom; M-S 2 .27-2.29 Angstrom), whereas the third sulfur of the thia crown ether o ccupies the apical position (Pd-S 2.81 Angstrom; Pt-S 2.82 Angstrom). The room-temperature H-1 NMR solution spectrum of each complex shows a n AA'BB' pattern in the methylene region. The NMR spectal properties o f [Pt(phen)([9]aneS(3))][PF6](2) between room temperature and -91 degr ees C in acetone-d6 solution are interpreted in terms of relativity ra pid intracomplex rearrangements (Delta G(double dagger) similar to 38 kJ mol(-1); T-c = -80 degrees C) similar to the nuclear motions associ ated with the formation and decay of the transition state in a Pt(II) associative substitution reaction.