Bridging tendency

Ni11 complexes of various amine/thiophenolate ligands have been investigated (for Ni complexes of ortho-aminothiophenol see Section 6.3.4.9.2(iv)). Thiophenolate is expected to exhibit decreased bridging tendency compared to aliphatic thiolates, but complexes (466) and (467) still consist of two pseudo-octahedral NiL fragments bridged via thiolate donors. In contrast to the parent complex (466), the thiolate and thioether donors in (467) coordinate cis to the Ni center... 

Deprotonated thioamides, which bind in the imino thiolate form (RN = CR-S ), exhibit a very low bridging tendency due to their lower S-basicity. If incorporated in a chelate scaffold with phenolate-O, it is the latter which forms the bridge, e.g., in (770).1940 1941... 

Compound 59 forms complexes of the type L(CuC1)2, L2CuBr2, L2PdCl2 IR spectra show coordination to be via the nitrogen lone pairs. They show a bridging tendency toward iron and molybdenum in, e.g., LFe2(CO)7 and [LMo(CO)4]2.72... 

Whereas electrophiles with strong bridging tendency (e.g., halogens) react considerably faster with alkenes than with analogously substituted alkynes, protons [209,210] and carbocations [211] have been reported to attack analogously substituted double and triple bonds with similar rates [212]. 

The thermal instability of iron ethoxide is related to the degree of association of the ethoxide molecule in the solid state. It is known that the corresponding aluminum compound is an infusible solid due to the extensive polymerization of Al(OEt)3 through alkoxy bridging. The bridging tendency in alkoxide species is governed by the propensity of the metal centers to increase their coordination state,which can be tuned either by increasing the steric bulk... 

If the connecting chain between phosphorus atoms is only one atom (e.g., dppm, 10, HC(PMe2)3, and HC(PPh2)3, H, or CH3Si(PPh2)3, 12), the phosphino units tend to bridge across two metals (see Chapters 4 and 5 for dppm examples). In fact, this bridging tendency has been used to... 

Thus, instead of condensation in case of metal oxide formation, the strong bridging tendency of fluoride ions causes the formation of three-dimensional nanoscopic particles under these conditions. 

---