Reactions of tris(triphenylphosphine)platinum(O). II. Preparation and properties of boron trichloride and aluminum trimethyl adducts of platinum(O)

Abstract

Treatment of [(C3H5)3P]3Pt with BCls affords [(C6H6)3P]3Pt•2BCls whereas [(CeHsLPLPt affords [(CeH5)3P]3Pt•2BCl3 and (CSH5)3P-BC13. Reaction of [(C6H5)3P]3Pt-2BCl3 with pyridine (py) yields py-BCl3 while pyrolysis of the adduct affords benzene. Treatment of [(C6H5)3P]2Pt'SiF4 with BC13 yields [(CeHslsPLPt'BCla whereas reaction with [A1(CH3)3L affords a paramagnetic Pt species and mixed fluoromethylsilanes. Reaction of [(C6H3)3Pj3Pt with [A1(CH3)3]2 results in the formation of [(CeHsLPLPt •2 1( 3)3 which readily decomposes in solution to yield two weakly paramagnetic species. One radical is associáted with Pt and the other with Al.3050 vw 1178 m 935 w 614 w 1582 w 1156 m, sh 840 w 539 vw 1570 vw 1092 s 750 s, sh 508 vs ("X" sensitive) 740 s 450 vw 1474 m 1024 w 704 s, sh 420 vw 1430 m 997 w 687 vs, b 1304 vw 970 vw

Δ4‐1,3,2‐Diazaborolines as Complex Ligands

“…26.2 18.3 [5] 'H-NMR, 6 [ppm] cs. TMS (in CDCls) CH 6.16 (2) 6.05 (2) ( I ,3-Di-tert-butyl-2-methyl-A4-1 ,3,2-diazaboroline)tricarbonylchromium (2) A mixture of (CH3CN)3Cr(C0)3 (2.26 g, 8.7 mmol) and ( I a ) (5.82 g, 30.0mmol) in dry dioxane saturated with nitrogen is heated in the absence of air for 6 h at 85°C.…”

Rotation of coordinated cyanoolefins in their adducts with some rhodium(I) isocyanide complexes

“…The methyl proton signal at t- 6.43 is a sharp singlet at 46", broadens as the temperature is lowered, coalesces at 33.0°, and splits into a doublet with a separation of 10.0 Hz at -8". The methyl proton signal at t- 6.43 is a sharp singlet at 46", broadens as the temperature is lowered, coalesces at 33.0°, and splits into a doublet with a separation of 10.0 Hz at -8".…”

“…This can be attributed to the profound relation of these compounds to homogeneous catalysis; as well as to the still controversial aspects of the chemical bonding involved in the ~y s t e m ,~ although the problem seems to be settled qualitatively? Rev.,6 ,2 7 ( 2 ) J . Especially, cyanoolefins are widely used as 71 acids,5 and the adducts isolated generally (1) .…”

Palladium(0)‐Catalyzed [2σ + 2π] Cycloadditions Methylenecyclopropane to Alkenes

“…Table I), up to 300mol ( I ) being converted per 1 mol Pd. The codimerization always has to compete with cyclodimerization of ( I ), which affords the 5-methylenespiro [2,4]heptane ( 5 ) . Only negligible amounts of other products are formed.…”

“…( l a ) (2) "B-NMR, 6 [ppm] 0s. BF3.0Etl (in CDC13) 26.2 18.3 [5] 'H-NMR, 6 [ppm] cs. TMS (in CDCls) CH 6.16 (2) 6.05 (2) …”