Oxidized Ruthenium Ferrocenylacetylide Complexes, [(.eta.-C5H5)L2RuCCFc]PF6 and [(.eta.-C5Me5)L2RuCCFc]PF6 (L = Phosphines). Electron-Delocalized Heterobinuclear Mixed-Valence Complexes

Abstract

The reaction of ferrocenylacetylene with (v-C5R5)LzRuCl [R = H or Me; LO = 2PPh3, Ph2-PCH2CH2PPh2 (dppe), or (Ph2PCsHd2Fe (dppf)] in the presence of NH4PF6 and the subsequent treatment with alkali gave ruthenium(I1) ferrocenylacetylide complexes (~-C~R~) L~R U C C F C in good yields. Cyclic voltammetric data suggest the large electron delocalization between the Fe atom of the ferrocene moiety and the Ru(I1) atom in their one-electron-oxidized complexes. The IR spectra of the oxidized ferrocenylacetylide complexes and the molecular structure of [ (v-C5H5)(Ph3P)2Ru(CCFc)]PF6 determined by X-ray diffraction gave an evidence for such electron delocalization. Crystallographic data for 12 are as follows: space group E d a , a = 17.176(9) A, b = 12.055(7) A, c = 22.480(9) A, P = 101.35(4)', V = 4563(4), 2 = 4. The complexesshowed low-energy absorption bands assigned to intervalence transfer transitions in the nearinfrared (NIR) region. The parameter a2, which shows the degree of ground-state delocalization

Long-distance electronic interaction in a molecular wire consisting of a ferrocenyl–ethynyl unit bridging two [(η5-C5H5)(dppe)M] metal centers

“…1, the ORTEP view confirms the molecular structure with the ferrocenyl group directly linked to the ethynyl linkage which is linked to the [(g 5 -C 5 H 5 )(dppe)Ru] metal center. Geometry of the [(g 5 -C 5 H 5 )-(dppe)Ru] fragment is similar to those examples reported previously, such as complex of [(g 5 -C 5 H 5 )(dppe)Ru(C"Cfc)] [29]. Distances of Ru-P (Ru1-P1, 2.2449(5); Ru1-P2, 2.2611(5)) and Ru1-C cp (Ru1-C11, 2.236(2); Ru1-C12, 2.227(2); Ru1-C13, 2.233(2); Ru1-C14, 2.247(2); Ru1-C15, 2.244(2)) are also within previously observed ranges.…”

Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes

“…Chemical oxidation of [Ru(CϵCFc)(dppf)Cp] and [Ru(CϵCFc)(PPh 3 ) 2 Cp*] also yields stable, isolable radical cations with spectroscopic features similarly consistent with the above observations. Chemical oxidation of the dppe-ligated congeners of these two complexes yielded only unstable, impure mixtures of oxidised material, [187] although low-temperature spectroelectrochemical experiments were able to satisfactorily characterise the oxidation products to be consistent with the above descriptions. [188] The underlying causes of the relative instability of the dppe-ligated complexes were not readily apparent from the experimental data, although the source of the difference is presumably electronic in nature.…”

“…In the most fundamental illustration of this premise one may consider the complex [Ru(CϵCFc)(PPh 3 ) 2 Cp] ·+ (Scheme 26). [187,188] Whereas the phenylethynylene complex [Ru(CϵCPh)(PPh 3 ) 2 …”

Octahedral hexanuclear silver(I) and copper(I) ferrocenylacetylide complexes

“…The octahedral hexanuclear acetylide complexes with M 2 M 0 4 (M ¼ Pt, Ir; M 0 ¼ Cu, Ag) cluster cores are usually linked by the alkyl or aryl acetylides in l-g 1 ,g 2 (r,p)-coordination mode. In no cases, the octahedral cluster cores are capped by l 3 -g 1 -coordinated acetylides.Ethynylferrocene (HCBCFc) is redox-active and versatile in design of donor-metal-acceptor (D-M-A) compounds with electron transfer properties [7][8][9][10][11][12][13][14][15][16]. The metal cluster complexes of ferrocenylacetylide, however, have been unexplored comparatively [17,18].…”