Reactions of haloalcohols with platinum(II)-alkynyl amd alkyne complexes. X-ray crystal structure of trans-[Pt(Me){C(OCH2CH2Cl)(CH(2)Ph)}(PPh(3))(2)][BF4]

The chloro complexes trans-[Pt(Me)(Cl)(PPh(3))(2)], after treatment with AgBF4, react with 1-alkynes HC=C-R in the presence of NEt(3) to afford the corresponding acetylide derivatives trans-[Pt(Me)(C=C-R)(PPh(3))(2)] (R=p-tolyl (1), Ph (2), C(CH3)(3) (3)). These complexes, with the exception of the t-butylacetylide complex, react with the chloroalcohols HO(CH2)(n)Cl (n=2,3) in the presence of 1 equiv. of HBF4 to afford the alkyl(chloroalkoxy) carbene complexes trans-[Pt(Me){C[O(CH2)(n)Cl](CH(2)R)}(PPh(3))(2)][BF4] (R=p-tolyl, n=2 (4), n=3 (5); R=Ph, n=2 (6)). A similar reaction of the bis(acetylide) complex trans-[Pt(C=C-Ph)(2)(PMe(2)Ph)(2)] with 2 equiv. HBF4 and 3-chloro-1-propanol affords trans-[Pt(C=CPh){C(OCH2CH2CH2Cl)(CH(2)ph)}(PMe(2)Ph)(2)][BF4] (7). The alkyl(chloroalkoxy)-carbene complex trans-[Pt(Me){C(OCH2CH2Cl)(CH(2)Ph)}(PPh(3))(2)][BF4] (8) is formed by reaction of trans-[Pt(Me)(Cl)(PPh(3))(2)], after treatment with AgBF4 in HOCH2CH2Cl with phenylacetylene in the presence of 1 equiv. of n-BuLi. The reaction of the dimer [Pt(Cl)(mu-Cl) (PMe(2)Ph)](2) with p-tolylacetylene and 3-chloro-1-propanol yields cis-[PtCl2{C(OCH2CH2CH2Cl)(CH2C6H4-p-Me)}(PMe(2)Ph)] (9). The X-ray molecular structure of (8) has been determined. It crystallizes in the orthorhombic system, space group Pna2(1), with a=11.785(2), b=29.418(4), c=15.409(3) Angstrom, V=4889(1) Angstrom(3) and Z=4. The carbene ligand is perpendicular to the Pt(II) coordination plane; the Pt-C(carbene) bond distance is 2.01(1) Angstrom and the short C (carbene)-O bond distance of 1.30(1) Angstrom suggests extensive electronic delocalization within the Pt-C(carbene)-O moiety.