Synthesis, Characterization and Reactivity of New (μ‐Aminocarbyne)diruthenium Complexes Containing Alkynylimino Ligands

Abstract

+ (R = Xy, RЈ = Tol, 3a; R = Bz, RЈ = Tol, 3b; R = Me, RЈ = Tol, 3c; R = Xy, RЈ = Ph, 4a; R = Bz, RЈ = Ph, 4b; R = Me, RЈ = Ph, 4c; R = Bz RЈ = H, 5; R = Xy, RЈ = nBu, 6; R = Xy, RЈ = [C(Me)=CH 2 ], 7), which contain an alkynylimino ligand, formed from addition of the acetylide to the Me 3 CCN ligand. Structural and spectroscopic studies show that all these complexes contain the two Cp ligands in a relative cis arrangement, whereas two isomers arise from the different orientation of the substituents on the bridging aminocarbyne µ-CN(Me)(R) when R ϶ Me.

Diiron-aminocarbyne complexes with amine or imine ligands: C–N coupling between imine and aminocarbyne ligands promoted by tolylacetylide addition to [Fe2{μ-CN(Me)R}(μ-CO)(CO)(NHCPh2)(Cp)2][SO3CF3]

“…This hypothesis, far from providing any exhaustive interpretation of the mechanism leading to the novel vinylidene-diaminocarbene 15, simply underlines the complexity of the reaction, which further emphasizes the attitude of dinuclear aminocarbyne complexes in promoting C-C and C-N bond formation [1,4,13,16].…”

“…Fe(1)-Fe(2) 2.5353(9) C(12)-O(12) 1.144(4) Fe(1)-C (12) 1.741(4) C(13)-C (14) 1.341(4) Fe(1)-C (11) 1.842(4) C(14)-C(22) 1.537(4) Fe(2)-C (11) 2.002(4) C(22)-N(1) 1.503(4) Fe(1)-C (13) 1.898 (3) N(1)-C(35) 1.353(4) Fe(2)-C (13) 1.906 ( of the g 1 :g 2 vinylidene-diaminocarbene [Fe 2 {l-g 1 :g 2 -C@C(Ph)C(Ph) 2 N(H)CN(Me)(Xyl)}(l-CO)(CO)(Cp 2 )]- (16), in lower yields (31%), whereas the corresponding reaction with CH 3 (CH 2 ) 3 C"CLi resulted in a mixture of decomposition products. The formation of 15 is worth some more comments.…”

“…H 3 ); 5 16,. 5.12, 4.47, 4.35 (s, 10H, Cp); 4.76, 4.44 (s, 3H, NMe); 2.74, 1.91 (s, 6H, Me 2 C 6 H 3 ); À0.41, À0.76 (s, 3H, NH 3 ); (Isomers ratio = 3) 13.…”

Growing the Molecular Architecture at Alkynyl(amino)carbene Ligands in Diiron µ‐Aminocarbyne Complexes

“…The aminocarbyne Xyl group is located on the opposite side to the aminocarbene, as previously found in similar diiron complexes ,. [10b], The Fe(1)–C(23) interaction [1.942(6) Å] shows considerable π character, and the C(23)–N(2) distance [1.323(7) Å] also indicates some π interaction between the carbene carbon and N(2).…”

“…[1,10b,13] The Fe(1)-C(23) interaction [1.942(6) Å] shows considerable π character, and the C(23)-N(2) distance [1.323(7) Å] also indicates some π interaction between the carbene carbon and N(2). (2) 2.5196 (13) Fe(1)-C(23) 1.942(6) Fe(1)-C (12) 1.895(6) Fe(2)-C(12) 1.933(6) Fe(1)-C (13) 1.867(6) Fe(2)-C(13) 1.877(6) Fe(2)-C (11) 1.743(7) C(13)-N(1) 1.320(7) C(11)-O (11) 1.156(7) C(12)-O(12) 1.188(6) C(23)-N (2) 1.323(7) C(23)-C(33) 1.433(8) C(33)-C(34) 1.196(8) C(34)-C(35) 1.428(8) Fe(1)-C(12)-Fe (2) 82.3 (2) Fe (1)-C(13)-Fe (2) 84.6(2) Sum at C (13) 359.4(7) Sum at N(1) 360.0(9) Sum at C (23) 360.0 (8) Sum at N(2) 359.9(9) C(23)-C(33)-C(34) 176.0(6) C(33)-C(34)-C(35) 173. 3(6) The IR spectra of 2a-c (in CH 2 Cl 2 ) each exhibit two bands due to the carbonyl ligands at around 1980 and 1790 cm -1 and an absorption diagnostic of the alkynyl group at around 2165 cm -1 .…”