Olefin metatheses in metal coordination spheres: Versatile new strategies for the construction of novel monohapto or polyhapto cyclic, macrocyclic, polymacrocyclic, and bridging ligands

The broad applicability of the title reaction is established through studie s of neutral and charged, coordinatively saturated and unsaturated, octahed ral and square planar rhenium, platinum, rhodium, and tungsten complexes wi th cyclopentadienyl, phosphine, and thioether ligands which contain termina l olefins. Grubbs' catalyst, [Ru(=CHPh)(PCy3)(2)(Cl)(2)], is used at 2-9 mo l% levels (0.0095-0.00042M, CH2-Cl-2). Key data are as follows: [(eta (5)-C 5H4(CH2)(6)CH=CH2)Re(NO)(PPh3)-(CH3)], intermolecular metathesis (95%); [(e ta (5)-C5H5)Re(NO)(PPh3)(E-(CH2CH=CH2)(2))](+) TfO- (E=S, PMe, PPh), format ion of five-membered heterocycles (96-64%; crystal structure E=PMe); [(eta (5)-C5Me5)Re(NO)(PPh-((CH2)(6)CH=CH2)(2))(L)](n+) nBF(4)(-) (L/n=CO/1, Cl/0 ), intramolecular macrocyclization (94-89%; crystal structure L=Cl); fac-[( CO)(3)Re(Br)(PPh2(CH2)(6)CH=CH2)(2)] and cis-[(Cl)(2)Pt(PPh2(CH2)(6)CH=CH2) (2)], intramolecular macrocyclizations (80-71%; crystal structures of each and a hydrogenation product); cis-[(Cl)(2)Pt(S(R)(CH2)(6)CH=CH2)(2)], intro -/intermolecular macrocyclization (R = Et, 55%/24%; tBu, 72%/<4%); trans-[( Cl)(L)M(PPh2(CH2)(6)-CH=CH2)(2)] (M/L = Rh/CO, Pt/C6F5) intramolecular macr ocyclization (90-83%; crystal structure of hydrogenation product, M=Pt); fa c-[W(CO)(3)(PPh-((CH2)(6)CH=CH2)(2))(3)], intramolecular trimacrocyclizatio n (83%) to a complex mixture of triphosphine, diphosphine/monophosphine, an d tris(monophosphine) complexes, from which two isomers of the first type a re crystallized. The macrocycle conformations, and basis for the high yield s, are analyzed.