140389-71-5

Upstream product

• 124686-50-6 5,5-diphenyl-5-(trimethylsiloxy)penta-1,3-diine 

Downstream Products

• 140389-73-7 Ru((C₆H₅)2PCH₂P(C₆H₅)2)2(C₃(OCH₃)CHC(C₆H₅)2)2⁽²⁺⁾*2BF₄^(1-) = Ru((C₆H₅)2PCH₂P(C₆H₅)2)2(C₃(OCH₃)CHC(C₆H₅)2)2(BF₄)2 

Relevant academic research and scientific papers

Metallacumulenes: Activation of diynes and formation of new allenylideneruthenium complexes. Crystal structures of trans-[(Ph2PCH2PPh2) 2(Cl)Ru=C=C=CR1R2]+ and trans-[(Ph2PCH2PPh2) 2Ru(=C=C=C(OMe)CH=CPh2)2]2+ derivatives

cis-RuCl2(Ph2PCH2PPh2) 2 (1) reacts with pentadiynes XC≡CC≡CCPh2(OSiMe3) [2 (X = H) and 3 (X = Bu3Sn)], but in the presence of NaPF6, to afford trans-(Ph2PCH2PPh2) 2(Cl)-RuC≡CC≡CCPh2(OSiMe3) (4). On protonation with HBF4 complex 4 in methanol leads to allenylidene trans-[(Ph2PCH2PPh2) 2(Cl)Ru=C-C=C(OMe)CH=CPh2]X (5a) (a: X = BF4) and in dichloromethane to trans-[(Ph2PCH2PPh2) 2(Cl)Ru=C-C=CCH=C(Ph)(o-C6H4)]X (6a) via electrophilic ortho-substitution within the metallacumulene intermediate LnRu=C=C=C=C= CPh2]X (A). Alternatively, complex 1 and diyne 2 with NaPF6 afford in one step allenylidenes 5b (b: X = PF6) in methanol and 6b in dichloromethane. Bis(diynyl) derivative trans-(Ph2-PCH2PPh2) 2Ru[(C≡CC≡CC(OSiMe3)Ph2]) 2 (7), obtained by reaction of 2 with 1 and HNiPr2, on protonation with HBF4 in methanol offered a direct route to the first bis(allenylidene) complex trans-[(Ph2PCH2PPh2) 2Ru(=C=C=C(OMe)CH=CPh2)2](BF4) 2 (8). The X-ray diffraction studies of two allenylidene complexes 6b and 8 are reported. The structure of 6b consists of two different allenylidene cations. That of 8 shows coplanar allenylidene ligands with a strong contribution of a ynyl resonance structure.