Intramolecular nucleophilic substitution transforms the phosphinate anions XCH2CH2(CH2)(n)CH2(Ph)P(O)O- (n = 0, 1; X = Br, Cl) (Et3NH+ salts; CH2Cl2 solution) into cyclic phosphinate esters 14 (n = 0, 1); unusually the five-membered ring product (n = 0) is formed only 4.3 (X = Br) or 5.7 (X = Cl) times faster than the six (n = 1). The analogous cyclisation of the thiophosphinate anions ClCH2CH2(CH2)(n)CH2(Ph)P(S)O- (n = 0, 1) gives the products 16 (n = 0, 1) with the sulfur atom in the ring; the five-membered ring is now formed 30 times faster than the six, still a rather modest rate advantage.

Tetrakis(organosilyl)bis(t-butyl isocyanide)platinum(IV) complex was prepared by reaction of 2,2-bis(disilanyl)dithiane with Pt3(CNtBu)6 through double oxidative addition of the two SiSi bonds to the platinum atom. In contrast, the reaction of hexamethyldisilane with the platinum(0) complex gave only the corresponding bis(trimethylsilyl)bis(t-alkyl isocyanide)platinum(II), which did not undergo further oxidative addition with hexamethyldisilane. Reactions of 2,2-bis(silylgermyl)dithiane with Pd(CNtBu)2 and Pt3(CNtBu)6 similarly afforded bis(organogermyl)palladium(II) and bis(organogermyl)bis(organosilyl)platinum(IV) complexes respectively.

In CH2Cl2 solution the phosphinate anion BrCH2CH2(CH2)(n)CH2(Ph)P(OO- cyclises only 4.3 times faster when n = 0 (five-membered ring product) than when n = 1; for the thiophosphinate anion ClCH2CH2(CH2)(n)CH2(Ph)P(SO- cyclisation (via sulfur) is still only 30 times faster when n = 0 than when n = 1.