Ruthenium(II) σ-acetylide complexes; monomers, dimers and polymers

Faulkner, Charlotte W.; Ingham, Scott L.; Khan, Muhammad S.; Lewis, Jack; Long, Nicholas J.; Raithby, Paul R.

doi:10.1016/0022-328x(94)88195-2

Cited by 83 publications

(27 citation statements)

References 15 publications

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“…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.…”

Section: Synthesismentioning

confidence: 98%

“…The conversion of cis-1 to the active five-coordinate species [RuCl(dppe) 2 ] + ([2] + ) takes place readily upon reaction with alkali metal salts including NaPF 6 [3] and KPF 6 [11], and salts of [2] + can be isolated from reaction of cis-1 with NaPF 6 [42,65], NaOTf or NaBPh 4 [66]. The conversion of trans-1 to salts of [2] + has been implicated under similar conditions, although the reaction is considerably slower [10,65].…”

Section: Synthesismentioning

confidence: 99%

“…Conversion of the thermodynamically stable isomer trans-1 to acetylide complexes trans-RuCl(C"CR)(dppe) 2 has been achieved following reaction of trans-1 with trialkylstannyl alkynes, sometimes in the presence of a CuI catalyst [6,54]. 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].…”

Section: Introductionmentioning

confidence: 99%

“…The chemistry of transition metal complexes transRuCl(C"CR)(dppe) 2 is very well established [1][2][3][4][5][6][7][8][9][10], with a considerable body of recent research demonstrating the utility of these moieties in the construction of multimetallic complexes [11][12][13][14][15], optical materials [16][17][18], including those that exhibit pH or redox-switchable NLO response [19][20][21][22][23][24][25], colormetric [26] and fluorescent [27] sensing behaviour, the ''wire-like" behaviour that arises from extensive d-p mixing along the Ru-C"C fragment [28][29][30][31][32][33][34][35][36][37], and other characteristics that make these compounds potentially useful molecular electronic components [5,33,34,[38][39][40][41]. The facile replacement of the chloride ligand in complexes trans-RuCl(C"CR)(dppe) 2 either directly or from related vinylidenes with a second alkynyl ligand is well documented …”

Section: Introductionmentioning

confidence: 99%

“…Initial reaction between cis-1 and NaPF 6 or similar salt in dichloromethane affords the five-coordinate species [RuCl(dppe) 2 ] + ([2] + ), which in turn reacts with terminal alkynes HC"CR to give the mono-chloro, monovinylidene species trans-[RuCl{C@C(H)R}(dppe) 2 ]PF 6 . Subsequent deprotonation of the vinylidene affords the corresponding neutral acetylide trans-RuCl(C"CR)(dppe) 2 (3) which can be isolated, or, in the presence of excess terminal alkyne, triethylamine and NaPF 6 , undergo further reaction to give the trans-bis(acetylide) complexes trans-Ru(C"CR) 2 (dppe) 2 (4).…”

Section: Introductionmentioning

confidence: 99%

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

Fox

Harris

Heider

et al. 2009

Journal of Organometallic Chemistry

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Section: Synthesismentioning

confidence: 98%

Section: Synthesismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

Fox

Harris

Heider

et al. 2009

Journal of Organometallic Chemistry

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Inorganic Polymers

Bourke¹,

Manners²

2001

Encyclopedia of Polymer Science and Technology

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The thermal ROP route requires the synthesis and careful purification of the cyclic trimer [Cl 2 PN] 3 and the use of elevated temperatures where control of molecular weight is very difficult and cross-linking can take place at high conversion, which can limit the yield. INORGANIC POLYMERSVol. 3to phosphazene polymers, which may well facilitate more rapid and extensive commercialization.Monomer Synthesis. Both the ROP and condensation routes to poly(dichlorophosphazene) require high purity monomers. For the traditional ROP process, ultrahigh purity [NPCl 2 ] 3 is required. The most common method for its preparation is through the reaction of PCl 5 with NH 4 Cl in a high boiling halogenated solvent, such as chlorobenzene or tetrachloroethane, at 150 • C. The yields can approach 70-80% under specialized conditions, but 50% is more typical (25). The phosphoranimine most commonly used in the aforementioned condensation route to poly(dichlorophosphazene) is Cl 3 P NSi(CH 3 ) 3 . The synthesis of this compound has been described (21) and is based on a modification of an earlier procedure (26) involving the reaction of PCl 5 with LiN(Si(CH 3 ) 3 ) 2 at −78 • C in hexane. However, the purification required by this method is a challenge and leads to an overall yield of <40%.It has also been reported that the reaction of N(Si(CH 3 ) 3 ) 3 with PCl 5 can be manipulated to maximize yields of either the cyclic trimer (76%) or the pure phosphoranimine monomer (40%) through variations in reaction conditions (25). These reactions use milder conditions than previously reported methods, with higher yields. In addition, the major side product, (CH 3 ) 3 SiCl, can be recycled to form one of the starting materials, N(Si(CH 3 ) 3 ) 3 .N-Silylphosphoranimines with alkyl and aryl substituents can be synthesized by reaction of commercial starting materials such as PCl 3 , ((CH 3 ) 3 Si) 2 NH, and Grignard reagents by way of a three-step process, with typical yields of 60-70%. These precursors are also accessible via a "one-pot" synthesis, which requires only isolation of the final product with yields of about 75% (3).Uses. Some of the most useful polyphosphazene derivatives are fluoroalkoxy derivatives, and amorphous copolymers are very useful as flame-retardant, hydrocarbon-solvent, and oil-resistant elastomers and have found aerospace and automotive applications. Polymers such as the amorphous comb polymer poly[bis(methoxyethoxyethoxy)phosphazene] (8) are of considerable interest as components of polymeric electrolytes in battery technology (1). Vol. 3 INORGANIC POLYMERS 35Polyphosphazenes are also of interest as biomedical materials and bioinert, bioactive, membrane-forming, and bioerodable materials (1).

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