mer,cis-Chlorotris(dimethylphenylphosphine)nitrido(trifluoromethylsulfonato)rhenium(V)

Kinetic Effects in Heterometallic Dinitrogen Cleavage

“…The white solid was removed by filtration, and the yellow supernatant was transferred to a fresh 20-mL vial. This solution contains mer-(PhMe 2 P) 3 Re(N)Cl(OTf), 18 which was characterized by 31 P{ 1 H} NMR (CDCl 3 ): δ -19.69 (t, J ) 14 Hz, 1P), -7.31 (br, 2P). PMe 2 Ph (Strem; 160 mg, 1.16 mmol) was added, and the vial was securely capped.…”

“…The former complex is known, 10 but the latter is not. It was prepared by metathesis of (PhMe 2 P) 3 -Re(N)Cl 2 14 with AgOTf to generate the pale-yellow complex mer-(PhMe 2 P) 3 Re(N)Cl(OTf), 18 whose presence was confirmed by 31 P{ 1 H} NMR. The addition of PMe 2 Ph to the triflate complex in situ yields cationic trans-[9]OTf, which is isolated as a pale-yellow air-stable salt (eq 5).…”

Synthesis and characterization of novel phosphinoketone and phosphinoenolato rhenium(v) nitrido complexes. Crystal structure of ReNCl2{iPr2PCH2C(Ph)O}2

“…In fact, bond lengths similar to ours have been observed in nitrido-Re() or -Tc() complexes for trans bonds with water (2.463 Å in [Re-N(CN) 4 (H 2 O)] 2Ϫ , 29 2.688(4) Å in TcNL(H 2 O), where L = 1,4,8,11-tetraazacyclotetradecane-5,7-dione, 30 2.481(4) Å in [TcN(pnao)(H 2 O)](BPh 4 ), where pnao Ϫ = 3,3,9,9-tetramethyl-4,8-diazaundecane-2,10-dione dioximate 31 ) or the poorlycoordinating triflate oxygen in ReNCl(PMe 2 Ph) 3 (O 3 SF) (2.403 Å). 32 The Re-P2 distance (2.458(2) Å) for the monodentate phosphinoketone is greater than that of the chelated ligand (2.438(2) Å), but both do not differ greatly from those found for the related enolate chelates. 9, 11 The Re-Cl distances are intermediate between those observed in the five-coordinate ReNCl 2 (PPh 3 ) 2 33 and in the six-coordinate ReNCl 2 (PMe 2 Ph) 3 compounds.…”