The reactions of anhydrous HX (X = Br, Cl) with trans-Mo(N2)2(triphos) (PPh3) (1) where triphos = PhP(CH2CH2PPh2)2, yield [MoX(NNH2)(triphos)(PPh3)]X as a mixture of isomers: 1A(X) and 1B(X). In solution, PPh3 dissociates rapidly from the B isomer. Addition of PPh3 to a mixture of 1A(X) and 1B(X) enabled the separation of the isomers by fractional crystallization. Addition of PPh2Me to a mixture of 1A(X) and 1B(X) led to the isolation of 1A(X) and [MoX(NNH2)(triphos)(PPh2Me)]X [2B(X)]. Amber 1A(Cl) crystallizes with one molecule of toluene in the monoclinic space group P21 with a = 13.714(2), b = 13.924(2), c = 14.279(3) Å, β = 102.44(1)°, and Z = 2. Olive-green 2B(Cl) crystallizes with two molecules of salvation; one each of pentane and toluene, in the triclinic space group P1 with a = 12.922(2), b = 13.552(3), c = 18.067(4) Å, α = 106.04(1), β = 107.65(1), γ = 97.22(1)°, and Z = 2. Loss of PPh3 from 1B(X) is proposed to be due to steric factors. Yields of ammonia and hydrazine formed from all the nitrogen hydride complexes are summarized.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry