Counterions bridging

The binding of multivalent counterions decreases the repulsion and causes attraction between polyions. This attraction is the result of the fluctuation of the counterion distribution and is equivalent to a multivalent counterion bridge between polyions. 

The bridging by bromine prevents rotation about the remaining bond and back-side nucleophilic opening of the bromonium ion by bromide ion leads to the observed anti addition. Direct evidence for the existence of bromonium ions has been obtained from NMR measurements.31 A bromonium ion salt (with Br3 as the counterion) has been isolated from the reaction of bromine with the very hindered alkene adamantylide-neadamantane.32... 

The Mn C [Mn6(OH)3Cl3(hmp)9]6 2+ (31) complex, where hmp is 2-hydroxymethylpyridine, is structurally very close to these two manganese rings. It is a mixed-valence manganese cluster with a central Mn2+ ion. A Cl- counterion is hydrogen-bonded to the p3-OH groups which bridge the six Mn ions. 

With diammonium ions [H3N(CH2) NH3]2+ (2 < n < 6) as counterions, several linear and layered polymeric Cd sulfates are generated. In the chain anion oo1[CdCl4/2(S04)2/2]2 ( = 2), octahedral units are linked by both /r-chloro and /r-sulfato bridges a similar structural situation is met in the compounds with oo1[CdX4/2(S04)2/2]2 anions (X = C1, Br n = 6). A layered structure of the anion oo2[Cd2(H20)2(S04)3T (n = 3) is achieved by linking two different octahedral CdOfi units by S04 bridges exclusively. 0... 

When rationalizing the significant difference of the hydrocarbon- and ether-bridged radical anions, the main aspect will certainly be the conformation of the oxyethylene chain, which brings the electrophores into closer contact. An additional aspect follows from the ability of the oxygen centres along the chain to chelate the counterion and thus to fix the cation between the electrophores. It is not possible from the available experimental evidence to discriminate between the two effects. The role of ion pairing and the relative position of the counterion and carbanion will be dealt with below. 

Treatment of 77 with one equivalent of [AuCl(tht)] (tht = tetrahydrothiophene) leads to the type III AuCl bridged pincer complex 79 in high yield (counterion is Cl ) [149]. The unique complex 79 is the only heterodimetallic compound with two metal atoms attached at a carbodiphosphorane carbon(O) atom. The environment at the central carbon atom is planar in 77 and pyramidal in 78 and 79. P-C bond lengths and P-C-P angles in the dication 78 are closely related to those in the neutral Pt complex 36 (Fig. 25). The two metals of 79 attached to the carbon atom are coimected via a very short d -d ° pseudo closed shell interaction with a Pd-Au bond length of 2.8900(3) A a similar bonding situation (aurophilic attraction) is found in the gold complex 29 shown in Fig. 23. 

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