Synthesis of ruthenium–rhodium heterobimetallic complexes via ring-opening reactions of bidentate phosphine ligands; crystal structures of [Ru(C5H5)Cl{Ph2PC(CH2)PPh2}] and [(C5H5)Ru(µ-CO)2{µ-Ph2PC(CH2)PPh2}RhCl2]

Brown, Michael P.; Burns, D.K.; Das, Ranjit Kumar; Dolby, P. Ann; Harding, Marjorie M.; Jones, R.W.; Robinson, E. J.; Smith, Anthony K.

doi:10.1039/dt9910000351

Cited by 15 publications

(2 citation statements)

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“…Perdeuterated solvents for NMR studies were used as received. The ligand dppen was prepared by the published method (tetrahydrofuran was used instead of benzene as solvent for Cl 2 CCH 2 ), as were [RuCl 2 (PPh 3 ) 3 ] and [CpRu(dppen)Cl] (Cp = η 5 -C 5 H 5 ) …”

Section: Methodsmentioning

confidence: 99%

“…Herein we report the syntheses and characterization of trans -[RuCl 2 (dppen) 2 ] ( 1 ) and cis -[RuCl 2 (dppen) 2 ] ( 2 ), their reactivity with primary and secondary amines, and the derivatization of electrode surfaces with the amine adduct trans -[RuCl 2 ({Ph 2 P} 2 CHCH 2 NH{CH 2 } 3 Si{OEt} 3 ) 2 ] ( 3e ). We also describe some attempts to extend this chemistry to the “half-sandwich” complex [CpRuCl(dppen)] ( 6 ; Cp = η 5 -C 5 H 5 ) …”

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confidence: 99%

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Nucleophilic Addition to Complexes of (Ph₂P)₂CCH₂as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

et al. 1997

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The ligand (Ph 2 P) 2 CdCH 2 (dppen) reacts with [RuCl 2 (PPh 3 ) 3 ] in CH 2 Cl 2 to give trans-[RuCl 2 (dppen) 2 ], 1. Complex 1 has reversible Ru(II)/Ru(III) electrochemistry, and on treatment with NOBF 4 , 1 affords [RuCl 2 (dppen) 2 ]BF 4 , 1 + . Refluxing solutions of 1 in chlorobenzene affords cis-[RuCl 2 (dppen) 2 ], 2. With excess RNH 2 in chlorobenzene or toluene, 1 reacts to give functionalized diphosphine complexes of general formula trans-principally by a small upfield shift in their 31 P{ 1 H} NMR spectra compared to that of 1 and by their distinctive 1 H NMR spectra. Complex 3b‚4MeOH crystallizes in the space group P1 h with a ) 11.448(6) Å, b ) 13.10(1) Å, c ) 11.178(7) Å, R ) 93.16(6)°, β ) 99.51(5)°, γ ) 92.19(5)°, V ) 1648(2) Å 3 , and D calcd ) 1.250 g cm -3 for Z ) 1. Complex 3e reacts with the surface hydroxyl groups of indium-doped tin oxide (ITO) electrodes, to give monolayers of anchored, redox-active Ru(II)-diphosphine complexes, characterized by cyclic voltammetry. The modified electrodes are stable to repetitive cycling over the Ru(II)/Ru(III) redox wave in acetonitriletetraethylammonium tetrafluoroborate and in aqueous buffer (pH 8). With anodized Pt electrodes, however, 3e reacts to form multilayers. Reaction of 1 with secondary amines is more sluggish than reaction with primary amines, and only adducts with pyrrolidine (3f) and morpholine (3g; impure) were isolated. With LiCtC(CH 2 ) 3 -CH 3 , 1 reacts to give trans-[Ru(CtCR) 2 ({Ph 2 P} 2 CHCH 2 CtCR) 2 ] (R ) n-butyl, 5); acetylide nucleophiles displace the chloride ligands as well as adding to the dppen double bonds of 1. Other carbanions fail to react with 1. The cis complex 2 reacts with a limited range of primary amines, to afford cis-[RuCl 2 ({Ph 2 P} 2 CHCH 2 NHR) 2 ] (R: n-hexyl, 4a; [CH 2 ] 3 Si[OEt] 3 , 4b). However, 4b was too insoluble for electrode derivatization. The "half-sandwich" complex [CpRuCl(dppen)] (6; Cp ) η 5 -C 5 H 5 ) also reacts with RNH 2 to give [CpRuCl({PPh 2 } 2 CHCH 2 NHR)] (R: -[CH 2 ] 3 NH 2 , 7a; -CH 2 Ph, 7b).

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Nucleophilic Addition to Complexes of (Ph₂P)₂CCH₂as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

et al. 1997

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Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane-Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds

Knorr

Jourdain

Gregorio

et al. 2002

Eur. J. Inorg. Chem.

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When [(OC) 3 Fe(µ-CO)(µ-dppm)PtCl 2 ] (1) is allowed to react with stoichiometric amounts of various isocyanides, cleavage of the metal−metal bond occurs, yielding the heterodinuclear isocyanide complexes [(OC) 4 Fe{µ-dppm}Pt(Cl) 2 (CNR)] (2a: R = 2,6-xylyl; 2b: R = o-anisyl; 2c: R = benzyl; 2d: R = cyclohexyl; 2e: R = tosylmethyl). Reduction of 2a−2e by NaBH 4 in the presence of PPh 3 affords the isocyanide-bridged complexes [(OC) 3 Fe(µ-C=N−R)(µ-dppm)Pt(PPh 3 )] (3a: R = 2,6-xylyl; 3b: R = o-anisyl; 3c: R = benzyl; 3d: R = cyclohexyl; 3e: R = tosylmethyl). Metathesis of 2a−2d with NaI rapidly results in the formation of [(OC) 4 Fe{µ-dppm}PtI 2 (CNR)] (4a−4d), which is slowly transformed under extrusion of CO giving [(OC) 2 IFe{µ-dppm}(µ-CO)PtI(CNR)] (6a: R = 2,6-xylyl; 6b: R =

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?Short-bite? ligands in cluster synthesis

Mague

1995

J Clust Sci

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Synthesis of ruthenium–rhodium heterobimetallic complexes via ring-opening reactions of bidentate phosphine ligands; crystal structures of [Ru(C₅H₅)Cl{Ph₂PC(CH₂)PPh₂}] and [(C₅H₅)Ru(µ-CO)₂{µ-Ph₂PC(CH₂)PPh₂}RhCl₂]

Cited by 15 publications

References 12 publications

Nucleophilic Addition to Complexes of (Ph₂P)₂CCH₂as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

Nucleophilic Addition to Complexes of (Ph₂P)₂CCH₂as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane-Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds

?Short-bite? ligands in cluster synthesis

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Synthesis of ruthenium–rhodium heterobimetallic complexes via ring-opening reactions of bidentate phosphine ligands; crystal structures of [Ru(C5H5)Cl{Ph2PC(CH2)PPh2}] and [(C5H5)Ru(µ-CO)2{µ-Ph2PC(CH2)PPh2}RhCl2]

Cited by 15 publications

References 12 publications

Nucleophilic Addition to Complexes of (Ph2P)2CCH2as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

Nucleophilic Addition to Complexes of (Ph2P)2CCH2as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane-Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds

?Short-bite? ligands in cluster synthesis

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Synthesis of ruthenium–rhodium heterobimetallic complexes via ring-opening reactions of bidentate phosphine ligands; crystal structures of [Ru(C₅H₅)Cl{Ph₂PC(CH₂)PPh₂}] and [(C₅H₅)Ru(µ-CO)₂{µ-Ph₂PC(CH₂)PPh₂}RhCl₂]

Nucleophilic Addition to Complexes of (Ph₂P)₂CCH₂as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

Nucleophilic Addition to Complexes of (Ph₂P)₂CCH₂as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes