Chemistry of iridium carbonyl cluster complexes. Synthesis, characterization and solid state structure of the phosphido carbonyl cluster [Ir6(CO)12(μ-CO)2(μ-PPh2)−
Tóm tắt
The phosphido-bridged cluster [Ir6(CO)14 PPh2]− has been obtained by reaction of [Ir6(CO)15]2− with PHPh2, in the presence of ferrocenium cation, followed by deprotonation. The anion was isolated as a salt of [N(PPh3)2]+ or K+ and its structure was determined by single crystal X-ray data analysis. The salt [N(PPh3)2][Ir6(CO)14PPh2] crystallizes in the triclinic space group P
$$\bar 1$$
witha = 11.835(1) Å,b = 15.007(1) Å,c = 18.766(2)_ Å; α = 78.779(7)°,β = 87.260(8)°,γ = 75.794(6)°,V = 3169.3(7) Å,Z = 2. The structure was solved by Direct Methods and Difference Fourier techniques and refined down toR andR
w values of 0.034 and 0.036, respectively, for 8003 observed reflections havingl > 3σ(I). The octahedral anion, of idealized C2 symmetry, possesses two distance Ir-P = 2.284 Å, formally acting as a three electron donor. Average bond distances (Å) and angles (degrees) are: Ir-Ir = 2.776, Ir-C
t
= 1.87, Ir-C
b
= 2.05, C
t
-O
t
= 1.14, C
b
-Ob= 1.17, Ir-P-Ir = 74.3°, Ir-C
t
-O
t
= 177°, Ir-C
b
-O
b
= 138°, Ir-C
b
-Ir = 84° (t = terminal,b = bridging).
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