Synthesis of Rhenium(V) 2,4,6-Trimethylbenzylidyne Complexes by Abstracting "O2-" from an Acyl with Triflic Anhydride

Alkyne Metathesis Reactions of Rhenium(V) Carbyne Complexes

“…The complex 12 is the first example of rhenium arylcarbyne complexes obtained by alkyne metathesis. Previously reported rhenium arylcarbyne complexes are usually obtained by electrophilic abstraction of aryl alkoxycarbene or acyl , complexes and dehydrogenation of methyl groups of toluene derivatives with electron-rich rhenium complexes. , For example, [CpRe­(CPh)­(CO) 2 ]­BCl 4 was synthesized by the reaction of CpRe­{C­(OMe)­Ph}­(CO) 2 with BCl 3 , [Re­(OTf)­{C­(2,4,6-C 6 H 2 Me 3 )}­(CO) 4 ]­OTf was prepared by the reaction of Re­{C­(O)­(2,4,6-C 6 H 2 Me 3 )}­(CO) 5 with (CF 3 SO 2 )­O, and ReH­(CPh)­(PNP) (PNP = ( i Pr 2 PCH 2 SiMe 2 ) 2 N) was obtained by the reaction of PhCH 3 with (PNP)­ReH 4 or (PNP)­ReH 2 (η 2 -cyclooctyne) …”

Tuning the Excited-State Properties of Luminescent Rhenium(V) Benzylidyne Complexes Containing Phosphorus and Nitrogen Donor Ligands

“…Following the work by Schrock and Williams on d 2 rhenium benzylidyne complexes, our studies have revealed that congeners bearing phosphine ligands exhibit a long-lived emissive excited state in fluid solution . We have continued to develop this theme with the purpose of (1) defining the nature of the emissive excited state in order to gain further insight into the photochemistry of metal benzylidyne complexes and (2) exploring the relationship between molecular structure and excited-state properties, such as excited-state energy, nonradiative and radiative decay rate constants, and excited-state redox potentials.…”

Haloacylation of the Quintuple‐Bonded Group VI Metal Amidinate Dimers and Disproportionation of Acyl Groups to Form Carbynes

“…As indicated by 1 H NMR spectroscopy, both of these two reactions proceed cleanly and unexpectedly yield solely the benzylidyne products [Mo 2 (X)(μ‐X)(μ‐CPh)(κ 2 ‐O 2 CPh){μ‐κ 2 ‐HC(N‐2,6‐ i Pr 2 C 6 H 3 ) 2 } 2 ] (X=Cl ( 8 ), Br ( 9 )) in good yields after 0.5 h stirring 24. 25 The steric effect is observed when 5 is treated with 1 equivalent of o ‐toluoyl chloride in diethyl ether, the bridging benzylidyne species [Mo 2 (Cl)(μ‐Cl)(μ‐C‐2‐MeC 6 H 4 )(κ 2 ‐O 2 C‐2‐MeC 6 H 4 ){μ‐κ 2 ‐HC(N‐2,6‐ i Pr 2 C 6 H 3 ) 2 } 2 ] ( 10 ) is also formed, but to expedite this reaction, it is carried out at 60 °C for 4 h to reach completion. Alternatively, the benzylidynes 8 – 10 can be directly prepared in good yields from the reactions of 1 with two equivalent of aroyl halides.…”