Substituent Effect on the Reactions of OsCl2(PPh3)3 with o‑Ethynylphenyl Carbonyl Compounds
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https://figshare.com/articles/dataset/Substituent_Effect_on_the_Reactions_of_OsCl_sub_2_sub_PPh_sub_3_sub_sub_3_sub_with_i_o_i_Ethynylphenyl_Carbonyl_Compounds/11848947
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Reactions of OsCl2(PPh3)3 with o-ethynylphenyl-carbonyl compounds o-HCCC6H4C(O)R (2, R = H (a) and Et (b)) produced the η3-o-ethynylphenyl-carbonyl complexes OsCl2(PPh3)2{η3-(o-HCCC6H4C(O)R)} (3). Treatment of OsCl2(PPh3)3 with o-HCCC6H4C(O)NEt2 (2c) produced the complex OsCl2(PPh3)2{CCH-o-C6H4C(O)NEt2)(CHCC6H4–C(O)NEt2)} (4c), which contains both a vinylidene and a vinyl or isobenzofuranyl carbene ligand. The structural data of 4c suggest that the complex can also be regarded as a metalated isobenzofurfuryl cation. Computational studies indicate that η3-o-ethynylphenyl-carbonyl complexes 3 are kinetically favored products, while complex 4c is a thermodynamically favored product. The substituent effect on the selectivity for the pathways leading to the formation of isomeric η3-o-ethynylphenyl-carbonyl complex OsCl2(PPh3)2{η3-(o-HCCC6H4C(O)R)}, 2-isobenzofuranyl carbene OsCl2{CH–CC6H4C(O)R}(PPh3)2, pyrylium OsCl2{−C(CH)C6H4C(O)R}(PPh3)2, and pyranylidene OsCl2{CCHC6H4C(O)R}(PPh3)2 from the complexes OsCl2(PPh3)2{η2-(o-HCCC6H4C(O)R)} (R = H and NEt2) has been investigated computationally.
创建时间：
2020-02-13
