Reactivity of Triruthenium Furyne and Thiophyne Clusters: Multiple Additions of Thiolato and Selenolato Ligands through Oxidative Addition of S–H and Se–H Bonds
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https://figshare.com/articles/dataset/Reactivity_of_Triruthenium_Furyne_and_Thiophyne_Clusters_Multiple_Additions_of_Thiolato_and_Selenolato_Ligands_through_Oxidative_Addition_of_S_H_and_Se_H_Bonds/2532940
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资源简介：
Reactions of 50-electron furyne and thiophyne clusters
Ru3(CO)7(μ-H)(μ3-η2-C4H2E){μ-P(C4H3E)2}(μ-dppm) (1, 2; E
= O, S) with thiols, dithiols, and benzeneselenol leads to the oxidative
addition of the E–H bonds followed by concomitant elimination
of the alkyne (probably as the alkene) to afford a range of new thiolato
and selenolato triruthenium complexes. Addition of PhSH or iPrSH in boiling benzene affords the 48-electron clusters Ru3(CO)5(μ-SR)2{μ-P(C4H3E)2}(μ-dppm)(μ-H) (3–6; E = O, S; R = Ph, iPr) resulting from the addition
of 2 equiv of thiol. In contrast, analogous reactions with 1,2-ethanedithiol
and 1,3-propanedithiol yield the 50-electron clusters Ru3(CO)3{μ-S(CH2)nS)2{μ-P(C4H3E)2}(μ-dppm)(μ-H) (7–10; E = O, S; n = 2, 3), in which four S–H
bonds have been activated. A similar multiple addition reaction is
seen upon addition of PhSeH to 1, affording the tetraselenolato
complexes Ru3(CO)4(κ1-SePh)(μ-SePh)3{μ-P(C4H3O)2}(μ-dppm)(μ-H)
(11) and Ru3(CO)3(μ-SePh)4{μ-P(C4H3O)2}(μ-dppm)(μ-H)
(12). Reaction of 2 with PhSeH gave the
tetraselenolato complex Ru3(CO)4(κ1-SePh)(μ-SePh)3{μ-P(C4H3S)2}(μ-dppm)(μ-H) (13)
together with bis(seleno)-capped Ru3(CO)5{PPh(C4H3S)2}(μ3-Se)2(μ-SePh)2(μ-dppm) (14) resulting
from further cleavage of two selenium–carbon bonds and formation
of a new carbon–phosphorus bond. The new clusters have been
characterized by a combination of analytical and spectroscopic methods,
and the molecular structures of 3, 4, 7, 8, and 11 have been determined
by single-crystal X-ray diffraction studies. Complexes 7–10 are examples of 50-electron clusters containing
three apparent metal–metal bonds; however, DFT calculations
carried out for 7 show that the longest metal–metal
interaction of 3.119 Å is actually held in place by the bridging
thiolato and diphosphine ligands and does not represent a direct metal–metal
bonding interaction.
创建时间：
2016-02-21
