Quaternization and oxidation reactions of cyclodiphosphazane derivatives and their copper(I) and gold(I) complexes

摘要

The reactions of cyclodiphosphazane derivatives cis-{~tBuN(H)P(μ-N~tBu)_2PN(H)~tBu} (1), cis-{MeN(C_4H_8N)P- (μ-N~tBu)_2P(NC_4H_8Me)} (2) and {(Me_2NCH_2CH_2O)P(μ-N~tBu)_2P(OCH_2CH_2NMe_2)} (3) with methyl iodide and methyl triflate and their subsequent reactions with elemental sulfur and selenium are reported. Interestingly, the reactions of 1-3 with an excess of methyl iodide resulted in quaternising only one phosphorus atom in cis-[{~tBuNHP(μ-N~tBu)_2P(CH_3)NH~tBu}](I) (4), two exocyclic nitrogen atoms and one of the phosphorus atoms in cis-{(Me_2NC_4H_8N)P(μ-N~tBu)_2P(CH_3)(NC_4H_8NMe_2)}](I)_3 (7) and only two exocyclic nitrogen atoms in cis-[{(Me3NCH_2CH_2O)P(μ-N~tBu)_2P(OCH_2CH_2NMe3)}](I)_2 (8). The reaction of 1 with one equiv. of methyl triflate produced cis-[{~tBuN(H)P(μ-N~tBu)_2P(CH_3)N(H)~tBu}]OTf (5), whereas the same reaction in a 1: 2 molar ratio afforded cis-{~tBuN(H)P(CH_3)(μ-N~tBu)_2P(CH_3)N(H)~tBu}(OTf)_2 (6). Compounds 4 and 5 showed poor solubility in water, whereas 7 and 8 were high melting crystalline solids with moderate to good water solubility. Treatment of 4 with either elemental sulfur or selenium gave both cis- and transchalcogenide derivatives. Similar reactions of 7 and 8 produced both mono- and bischalcogenides. Reactions between 4 or 7 and CuI yielded dinuclear complexes, cis-[{Cu2(μ-I)3(~tBuN(H)P)(μ-N~tBu)2(P(CH_3)N- (H)~tBu)]_2}(I)] (15) and cis-[{Cu_2(μ-I)_3[(Me_2NC_4H_8N)P(μ-N~tBu)_2P(CH_3)(NC_4H_8NMe_2)]_2}(I)5] (16), while the reaction of 8 with CuI produced a coordination polymer [{Cu2(μ-I)3(μ-N~tBuP)2(OCH_2CH_2NMe_3)_2}I]_∞ (17), containing triiodo-bridged [Cu_2(μ-I)_3] linkers. The molecular structures of several of these compounds were confirmed by single crystal X-ray diffraction studies. The Cu~I?Cu~I distance of 2.55 ? in 15 is quite short and is the same as that found in copper metal and also in complexes containing [Cu_2(μ-I)_3] linkers. All the metal complexes exhibit strong intra-, inter- or both intra- and inter-molecular hydrogen bonding interactions.