86013-28-7

Upstream product

• 12116-66-4 bis(cyclopentadienyl)hafnium dichloride 
• 65567-06-8 lithium diphenylphosphide 

Downstream Products

• 12116-66-4 bis(cyclopentadienyl)hafnium dichloride 
• 112896-14-7 (Cp)2(hafnium)(μ-PPh2)2(iridium)H(CO)(PPh3) 
• 112896-15-8 (Cp)2(hafnium)(μ-PPh2)2(rhodium)H(CO)(PPh3) 
• 109011-90-7 (C₅H₅)2Hf(SP(C₆H₁₁)2)2 
• 109011-89-4 (C₅H₅)2Hf(SP(C₆H₅)2)2 
• 100113-61-9 (C₅H₅)2Hf(P(C₆H₅)2)2Rh(C₉H₇) 

Relevant academic research and scientific papers

Transition Metal-Phosphide Chemistry: Synthesis of (M(η-C5H5)2(PR2)2) (M=Zr, R=Ph; M=Hf, R=Ph or cyclo-C6H11) and ((M(η-C5H5)2(PR2))2) (M=Ti, R=Ph or Me; M=Zr or Hf, R=Me), and their Reactions with Protic and Halogen-containing Species

Reactions of the metallocene dichlorides (M(cp)2Cl2) (M=Ti, Zr, or Hf; cp=η-C5H5) with stoicheiometric amounts of LiPR2 (R= Me, Ph, or cyclo-C6H11) yield either the direct exchange products (M(IV)(cp)2(PR2)2) (M=Zr, R=Ph; M=Hf, R=Ph or C6H11) or the reduced species ((M(III)(cp)2 (PR2))2) M=Ti, R=Me or Ph; M=Zr or Hf, R=Me).Spectral (i.r. and (1)H n.m.r.) characterisation of these compounds is presented and discussed with suggestions of possible structures.Treatment of (Zr(cp)2(PPh2)2) with PPh3Cl affords the 'mixed' chloro-phosphido-compound (Zr(cp)2Cl(PPh2)).Reactions of both the M(IV) and M(III) species with halogen-containing and protic reagents have been investigated.Each series reacts with smooth cleavage of the M-P bond(s), but whereas the compounds (M(cp)2(PR2)2) (M=Ti, Zr, or Hf) show simple metathetical exchange, ((M(cp)2(PR))2)usually (and in the case of M=Zr or Hf exclusively) also incorporate metal oxidation M(III) M(IV) into their reactions.

Characterization and interconversion of metal-phosphorus single and double bonds: Bis(cyclopentadienyl)zirconium and -hafnium bis(diorganophosphide) complexes

Two equivalents of LiPR2 react with (η-C5H5)2MCl2, affording (η-C5H5)2M(PR2)2 (M = Zr, Hf; R = ethyl, cyclohexyl (Cy), or phenyl). 31P NMR and X-ray structural results indicate that these complexes contain both single and double metal-phosphorus bonds which interconvert in solution. Sodium naphthalenide reduction of these complexes produces the corresponding ZrIII and HfIII complexes [(η-C5H5)2M(PR2)2] [Na(THF)n]; a bis(μ-diorganophosphido) heterobimetallic structure is proposed.