Synthesis and characterisation of mono-acetylide and unsymmetrical bis-acetylide complexes of ruthenium and osmium: X-ray structure determinations on [(dppe)2Ru(Cl)(CC–C6H4-p-NO2)], [(dppe)2Ru(Cl)(CC–C6H3-o-CH3-p-NO2)] and [(dppm)2Os(CC–C6H4-p-CH3)(CC–C6H4-p-NO2)]

Linear Optical, Quadratic and Cubic Nonlinear Optical, Electrochemical, and Theoretical Studies of “Rigid‐Rod” Bis‐Alkynyl Ruthenium Complexes

“…Complexes possessing the same number of PE groups at each alkynyll igand,b ut with different functionalization of these ligands, have also been explored. Interestingly,t he complexes trans-[Ru{(CC-1,4-C 6 H 4 ) n NO 2 }(CCR)(dppe) 2 ]( n = 1, R = 1,4-C 6 H 4 NEt 2 (3), Ph (16), 1,4-C 6 H 4 NO 2 (18)) exhibit similare xperimental and two-level correctedq uadratic nonlinearities (and the data for 18 are not zero/closet oz ero, as may have been anticipated for an apparently centrosymmetric molecule). We believe that the low barrier to rotationofthe phenylalkynyl ligandsr esults in contributions from (pseudo) D 2 octupolar symmetry (and thereby non-centrosymmetric) structuresi n which the planeso ft he alkynyl ligand aryl groups proximal to the metal centera re orthogonal;s imilar observations with porphyrin-based assemblies are extant.…”

“…[14c, j, 17] Ta ble 1s ummarizes resultso fc yclic voltammetric studies for ruthenium-alkynyl complexes 1-10,t ogether with data acquireds imultaneously from the relatedc omplexes 14-18;d ata for 11-14 have been reportedp reviously and those for 14 are in agreement with the present data. [18,19] It is widely accepted that the HOMO in such ruthenium-alkynyl complexes has considerable contribution from the metal-adjacent phenylalkynyl group, in addition to the expected metal character, [14j, 19] but forc onciseness we have labeled the first oxidationp rocesses as Ru II/III ;w e emphasize that this simplification shouldb eb orne in mind. The Ru II/III oxidation processes for the non-functionalized chloro-alkynyl complexes are typically reversible, occurring at potentials of approximately 0.55 Va nd invariant on p-system lengthening by addition of further phenylene ethynylene units (proceeding from 14 to 15 and then to 1).…”

A simple synthesis of trans-RuCl(CCR)(dppe)2 complexes and representative molecular structures

“…In the course of this work, single crystals of [2]OTf, 3b, 3c (as both 0.5THF and 2CH 2 Cl 2 solvates) and 3e suitable for X-ray diffraction were obtained, those of 3a [6], 3f [55], and the related complexes trans-RuCl(C"CC 6 H 3 -Me-2-NO 2 -4)(dppe) 2 [55], transRuCl(C"CC 6 H 4 CHO-4)(dppe) 2 [24], trans-RuCl(C"CC 6 H 4 F-4)(dppe) 2 [17], trans-RuCl(C"CC 6 H 4 F-3)(dppe) 2 [35] and trans-RuCl(C"CC 6 H 4 CH@CHC 6 H 4 NO 2 -4)(dppe) 2 [24] having been reported earlier. Crystallographic data and important bond lengths and angles are summarized in Tables 3 and 4, with plots of [2] [78].…”

“…At ambient temperature in dichloromethane under normal laboratory lighting conditions, mixtures of cis-1 and trans-1 are obtained in ca. 3:1 ratio (estimated here from integration of 31 P NMR resonances) over the course of approximately 1 h [6,10,39,55,63,64]. By lowering the temperature to 0°C, the ratio of cis-1:trans-1 can be increased as high as 10:1, although the reaction becomes very slow, taking well over 24 h for complete conversion.…”

“…Prolonged (5-7 day) reaction of the trans-1 with terminal alkynes in the presence of NaPF 6 followed by deprotonation of the resulting vinylidene has also been shown to afford mono-acetylide complexes transRuCl(C"CR)(dppe) 2 [55], the conversion of trans-1 to the active 16-electron species [RuCl(dppe) 2 ] + under these conditions being rather slow [10,56].…”