Carbon-rich dinuclear ruthenium bisallenylidene complexes

A variety of rigid ruthenium and osmium allenylidene [M 1 Cl(PP) 2 ＝ C ＝ C(4,5-diazafluoren-9-yl)-{M 2 (CHC(PPh 3 )CHC(PPh 3 )Cl 2 (PPh 3 ) 2 }][PF 6 ] 3 (4a: M 1 ＝Os, M 2 ＝Os, PP＝dppm; 4b: M 1 ＝Os, M 2 ＝Ru, PP＝ dppm; 4c: M 1 ＝Ru, M 2 ＝Os, PP＝dppe; 4d: M 1 ＝Ru, M 2 ＝Ru, PP＝dppe), ruthenium alkynyl-allenylidene complexes trans-[(dppe) 2 Ru(C≡CPh)Ru＝C＝C(R)][PF 6 ] (6a: R＝fluoren-9-yl; 6b: R＝4,5-diazafluoren-9-yl), trans-{(dppe) 2 [＝C＝C(fluoren-9-yl)]Ru(C≡C-R-C≡C)Ru[(＝C＝C(fluoren-9-yl)(dppe) 2 ]} [PF 6 ] 2 (8a, R＝ 1,4-phenylene; 8b, R＝1,3-phenylene) terminated by 4,5-diazafluoren-9-yl and fluoren-9-yl group have been prepared. These allenylidene complexes were derived from 9-ethynyl-9-fluorenol and 9-hydroxy-9-ethynyl-4,5-diazafluorene in the presence of cis-OsCl 2 (dppm) 2 and cis-RuCl 2 (dppe) 2 . The respective products have been fully characterized by 1 H, 13 C, 31 P NMR spectrometry, IR spectrometry, elemental analysis, and UV/Vis spectrophotometry. Moreover, electrochemical studies reveal that the dinuclear complexes display a quasi-reversible redox behavior and a moderate electronic communication between the two metal centers in 8a. UV-Vis studies show a remarkable absorption in the region (λ max ＝300-700 nm) for these complexes.

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Synthesis, Characterization and Electrochemical Properties of 4,5‐Diazafluoren‐9‐yl or Fluoren‐9‐yl Terminated Homobimetallic Ruthenium and Osmium Allenylidene, Alkynyl‐Allenylidene Complexes

Huang

Zhou

Zhao

et al. 2017

Chin. J. Chem.

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The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2016

Herndon

2018

Coordination Chemistry Reviews

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Through-conjugation of two phosphaalkyne (‘CP’) moieties mediated by a bimetallic scaffold

Leech

Crossley

2018

Dalton Trans.

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Through-conjugation of two phosphaalkyne moieties within an isolable molecule is demonstrated for the first time with the synthesis of [{Ru(dppe)2}2{μ-(C[triple bond, length as m-dash]C)2C6H4-p}(C[triple bond, length as m-dash]P)2], via base-induced desilylation of [{Ru(dppe)2}2{μ-(C[triple bond, length as m-dash]C)2C6H4-p}(η1-P[triple bond, length as m-dash]CSiMe3)2]2+. The nature of the cyaphide ligands and their influence upon the bimetallic core are studied electrochemically.

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Carbon-rich dinuclear ruthenium bisallenylidene complexes

Cited by 6 publications

References 32 publications

Synthesis, Characterization and Electrochemical Properties of 4,5‐Diazafluoren‐9‐yl or Fluoren‐9‐yl Terminated Homobimetallic Ruthenium and Osmium Allenylidene, Alkynyl‐Allenylidene Complexes

Synthesis, Characterization and Electrochemical Properties of 4,5‐Diazafluoren‐9‐yl or Fluoren‐9‐yl Terminated Homobimetallic Ruthenium and Osmium Allenylidene, Alkynyl‐Allenylidene Complexes

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2016

Through-conjugation of two phosphaalkyne (‘CP’) moieties mediated by a bimetallic scaffold

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