Joseph G. Morse

Photoreactions of tetrafluorodiphosphine with partially fluorinated ethenes

Abstract The photoreactions of tetrafluorodiphosphine with partially fluorinated ethenes have been observed to result in the formation of 1,2-bis(diflourophosphino) -1-fluoroethane, 1,2-bis(difluorophosphino)-1,1-difluoroethane, and 1,2-bis(difluorophosphino)-1,1,2-trifluoroethane. A rapidly diminishing yield of product results with increasing fluorination of the olefin.

Photoreactions of tetrafluorodiphosphine with alkynes

Abstract The reactions of tetrafluoridiphosphine with several alkynes in the gas phase and under UV irradiation were studied. Simple addition products were obtained in substantial yield from CF 3 CCH, CF 3 CCCH 3 , and CF 3 CCCF 3 . Methyl substituted alkynes gave little volatile product while ethyne and diphenyl ethyne gave no volatile addition products. Non-volatile byproducts were obtained, probably polymers, in substantial quantity in the latter instances. Volatile products were characterized by IR and NMR spectra and by mass spectrometry.

Coordination chemistry of bidentate diflourophospines IV. Complexes of 1,2-bis(diflourophosphino)ethane with Ni(O) and Mo(O).

The ligand, 1,2-bis(difluorophosphino)ethane, (PF2C2H4PF2), reacts with Ni(CO)4 in the gas phase and in solution to produce carbon monoxide and a polymer, [Ni(PF2C2H4PF2)2]x. PF2C2H4PF2 displaces norbornadiene from (C7H8)Mo(CO)4 to yield the relatively air-stable complex, Mo(CO)4-(PF2C2H4PF2). Analysis of the infrared spectrum of the monomeric complex indicates that the ligand exhibits π-acceptor strength equal to PF2C6H10PF2.

Dehydrohalogenation of adducts of dichloro(pentafluorophenyl)borane with mesidine and p-anisidine: a reinvestigation

La pyrolyse du borane du titre avec la mesidine ou la p-anisidine donne des aminoboranes, (aminoboryl) aminoboranes ou des bis(amino) boranes selon la duree de la pyrolyse. La deshalogenhydratation chimique avec le bis-dimethylamino-1,8 naphtalene conduit directement aux bis-(amino) boranes

SYNTHESES AND REACTIONS OF HALOPHOSPHINE COMPLEXES OF GROUP 7 TRANSITION METALS (Mn AND Re)

Abstract The photochemical reactions of the “piano stool” complexes CpMn(CO)3, CpRe(CO)3, and Cp∗ Mn(CO)3 (Cp∗ = η5-C5Me5) with the bidentate halophosphine ligand 1,2-bis(dichlorophosphino)ethane, Cl2PCH2CH2PCl2 (dcpe), gave the chelate complexes CpMn(CO)dcpe (1), CpRe(CO)dcpe (2), and Cp∗ Mn(CO)dcpe (3), respectively. Reactions of the dihalophosphine complexes 1,2 with excess F1- and MeO1- gave the substituted compounds CpM(CO)(R2PCH2CH2PR2) (4, M = Mn, R = F; 5, M = Mn, R = MeO; 6, M = Re, R = F). The ligand-bridged bimetallic complexes [CpM(CO)2](μ-dcpe)[(CO)2M′Cp] (9, M,M′ = Mn; 10, M,M′ = Re; 11, M = Mn, M′ = Re) were prepared by treatment of the dangling compounds CpM(CO)2 dcpe (7, M = Mn; 8, M = Re) with the solvento complex CpM′(CO)2(THF) (M′ = Mn or Re). The crystal structures of 1, 2, and 6 were determined by single crystal X-ray structure analyses. 1: monoclinic, P21/c, a = 12.008(2) A, b = 15.685(2) A, c = 14.980(2) A, β = 91.01(2)°, V = 2821.0(6) A3, Z = 8, R = 0.046; 2: monoclinic, P21/c, a ...

Dipole moments of the methylethylphosphines

Abstract The dipole moments of the methylethylphosphines have been determined by the Debye method in the gas phase. Values obtained are: CH 3 C 2 H 5 PH, 1.28 ± 0.04 D; (CH 3 ) 2 C 2 H 5 P, 1.31 ± 0.09 D; CH 3 (C 2 H 5 ) 2 P, 1.58 ± 0.12 D. These results are found to be generally consistent with the Weaver-Parry model (1966) for variation in phosphine dipole moments with substituents.