三2过渡金属有机.ppt

* Main group alkyl DHf (kcal/mol) BDE (kcal/mol) TM alkyl BDE (kcal/mol) CMe4 SiMe4 GeMe4 SnMe4 PbMe4 -40 -59 -17 -5 +32 86 75 60 52 36 Ti(CH2tBu)4 Zr(CH2tBu)4 Hf(CH2tBu)4 TaMe5 WMe6 47 60 64 62 38 Binding modes * General trends M-C bond enthalpy increases within a TM group. In main group alkyls, the M-C bond enthalpy decreases down in a group. M-C: 35-70 kcal/mol Similar to main group alkyl bond strength. Comparable to the strength of a C-I bond. The instability of TM alkyls is kinetic not thermodynamic. One strategy to isolate TM alkyls is to block available orbitals by using coordinati