TY - JOUR
T1 - The synthesis of a dinuclear anionic carbonyl derivative of manganese, [n(PPh3)2][Mn2(μ-PPh2)(CO) 8], and its reactions with complexes of Group 1B and Group 8A metals to give mixed-metal clusters
T2 - Comparative study of the X-ray crystal structures of...
AU - Iggo, Jonathan A.
AU - Mays, Martin J.
AU - Raithby, Paul R.
AU - Henrick, Kim
PY - 1984/12/31
Y1 - 1984/12/31
N2 - full title: The synthesis of a dinuclear anionic carbonyl derivative of manganese, [n(PPh3)2][Mn2(μ-PPh2)(CO) 8], and its reactions with complexes of Group 1B and Group 8A metals to give mixed-metal clusters: Comparative study of the X-ray crystal structures of [n(PPh3)2][Mn2(μ-PPh2)(CO) 8], [mn2{μ-Au(PMe2Ph)}(μ-PPh 2)(CO)8], and [mn2(μ-H)(μ-PPh 2)(CO)8] The first anionic dinuclear carbonyl derivative of manganese, [Mn 2(μ-PPh2)(CO)8]-, has been prepared by deprotonation of [Mn2(μ-H)(μ-PPh 2)(CO)8] (1) and isolated as its bis(triphenylphosphine)- iminium salt, [N(PPh3)2][Mn2(μ-PPh 2)(CO)8] (2). Complex (2) reacts with complexes of Group 1B and Group 8A metals to give the mixed-metal complexes, [Mn 2(μ-ML)(μ-PPh2)(CO)8] [M = Cu, L = PEt3 (3a); M = Ag, L = PEt3 (3b); M = Au, L = PMe 2Ph (3c); M = Au, L = PPh3 (3d); M = Au, L = PEt 3 (3e)], and [Mn2{μ-M(PPh3)L}(μ-PPh 2)(CO)8] [M = Rh, L = PPh3 (4a); M = Ir, L = CO (4b)]. Complex (3e) ionises in solution in the presence of excess PEt 3 to give [Au(PEt3)2]+ and [Mn 2(μ-PPh2)-(CO)8]-. The crystal structures of (2) and (3c) have been determined and are discussed in relation to that of (1), the structure of which has been redetermined in a different crystalline modification to that previously reported, and to a greater degree of accuracy than that originally achieved. Crystals of (1) are Triclinic, space group C1, with a = 8.157(2), b = 19.246(3), c = 14.510(2) Å, β = 89.10(3), β = 106.31 (3), γ = 90.07(3)°, Z = 4; 2 710 reflections with I ≥ 3σ(I) [3 < θ < 25°], refined to R = 0.0493 and R′, = 0.0506. Complex (2) crystallises in space group P21/c with a = 10.172(2), b = 30.441(4), c = 17.076(3) Å, β = 100.88(3)°, Z = 4; 4 005 reflections [I ≥ 3σ(I), 3 < θ < 25°], refined to R = 0.067 and R′ = 0.063. Crystals of (3c) are Monoclinic, space group P21/c, a = 13.360(2), b = 14.645(1), c = 17.336(3) Å, β = 115.20(1)°, Z = 4; 1 843 reflections [I ≥ 2σ(I), 3 < θ < 22.5°], refined to R = 0.079 and R′ = 0.065.
AB - full title: The synthesis of a dinuclear anionic carbonyl derivative of manganese, [n(PPh3)2][Mn2(μ-PPh2)(CO) 8], and its reactions with complexes of Group 1B and Group 8A metals to give mixed-metal clusters: Comparative study of the X-ray crystal structures of [n(PPh3)2][Mn2(μ-PPh2)(CO) 8], [mn2{μ-Au(PMe2Ph)}(μ-PPh 2)(CO)8], and [mn2(μ-H)(μ-PPh 2)(CO)8] The first anionic dinuclear carbonyl derivative of manganese, [Mn 2(μ-PPh2)(CO)8]-, has been prepared by deprotonation of [Mn2(μ-H)(μ-PPh 2)(CO)8] (1) and isolated as its bis(triphenylphosphine)- iminium salt, [N(PPh3)2][Mn2(μ-PPh 2)(CO)8] (2). Complex (2) reacts with complexes of Group 1B and Group 8A metals to give the mixed-metal complexes, [Mn 2(μ-ML)(μ-PPh2)(CO)8] [M = Cu, L = PEt3 (3a); M = Ag, L = PEt3 (3b); M = Au, L = PMe 2Ph (3c); M = Au, L = PPh3 (3d); M = Au, L = PEt 3 (3e)], and [Mn2{μ-M(PPh3)L}(μ-PPh 2)(CO)8] [M = Rh, L = PPh3 (4a); M = Ir, L = CO (4b)]. Complex (3e) ionises in solution in the presence of excess PEt 3 to give [Au(PEt3)2]+ and [Mn 2(μ-PPh2)-(CO)8]-. The crystal structures of (2) and (3c) have been determined and are discussed in relation to that of (1), the structure of which has been redetermined in a different crystalline modification to that previously reported, and to a greater degree of accuracy than that originally achieved. Crystals of (1) are Triclinic, space group C1, with a = 8.157(2), b = 19.246(3), c = 14.510(2) Å, β = 89.10(3), β = 106.31 (3), γ = 90.07(3)°, Z = 4; 2 710 reflections with I ≥ 3σ(I) [3 < θ < 25°], refined to R = 0.0493 and R′, = 0.0506. Complex (2) crystallises in space group P21/c with a = 10.172(2), b = 30.441(4), c = 17.076(3) Å, β = 100.88(3)°, Z = 4; 4 005 reflections [I ≥ 3σ(I), 3 < θ < 25°], refined to R = 0.067 and R′ = 0.063. Crystals of (3c) are Monoclinic, space group P21/c, a = 13.360(2), b = 14.645(1), c = 17.336(3) Å, β = 115.20(1)°, Z = 4; 1 843 reflections [I ≥ 2σ(I), 3 < θ < 22.5°], refined to R = 0.079 and R′ = 0.065.
UR - https://www.scopus.com/pages/publications/51149207176
U2 - 10.1039/DT9840000633
DO - 10.1039/DT9840000633
M3 - Article
AN - SCOPUS:51149207176
SN - 1472-7773
SP - 633
EP - 641
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 4
ER -