Synthesis and structures of [S=(H)P(µ-NR)]2, potential building blocks for inorganic phosphorus-sulfur macrocycles.

The reactions of the chloro-phosph(iii)azane dimers [ClP(µ-NR)]2 with LiSH give the dimers [S[double bond, length as m-dash](H)P(µ-NR)]2 (), which are potential new building blocks for inorganic macrocycles of the type [{P(µ-NR)}2(µ-S)]n. NMR spectroscopic studies and DFT calculations show that the preference for the cis or trans isomers of is largely influenced by the steric demands of the R-group, with cis isomers being preferred for bulky substituents. This is an important factor in regard to applications in macrocycle synthesis since the cis arrangement is pre-organized for cyclisation.

Synthesis and Hydrolytic Studies on the Air-Stable [(4-CN-PhO)(E)P(µ-N(t)Bu)]2 (E = O, S, and Se) Cyclodiphosphazanes.

Reaction of 4-CN-PhOH with [ClP(µ-N(t)Bu)]2 (1) (2:1 ratio) in the presence of Et3N produced the functionalized cyclodiphosph(III/III)azane [(4-CN-PhO)P(µ-N(t)Bu)]2 (2). Oxidation of 2 produced cyclodiphosph(V/V)azanes [(4-CN-PhO)(E)P(µ-N(t)Bu)]2 [E = O (3), S (4), and Se (5)]. This is the first example of a series of cyclodiphosph(V/V)azane derivatives obtained from a single cyclophosph(III/III)azane precursor where all the accessible chalcogen oxidized products are air-stable over prolonged periods of time.

The regioselective photochemical rearrangement of alpha-[PN(t)Bu](4).

The photochemical dyotropic (two-bond shift) rearrangement of the phosphazane cage alpha-[PN(t)Bu](4) (alpha) into the isomer beta-[PN(t)Bu](4) (beta) occurs via a multi-step radical mechanism; the structures of the alpha and beta isomers are directly analogous to isovalent alpha- and beta-As(4)S(4) and P(4)S(4).

Joining the crown family; the tetrameric, O-bridged macrocycle [{P(micro-N(t)Bu)}2(micro-O)]4.

The in situ reaction of the dianion [O_P(micro-N(t)Bu)]2(2-) with the dimer [ClP(micro-N(t)Bu)]2 gives the O_bridged macrocycle [{P(micro-N(t)Bu)}2(micro-O)]4 (1), being the largest crown-like phosph(III)azane of its type to be reported and having a structure that is directly related to the ubiquitous 12-crown-4.

Synthesis and structure of the Li13 cage [[[O-P(mu-NtBu)]2Li2]3(LiCl)6Li(Cl/OnBu)0.5(thf)7], containing a [O-P(mu-NtBu)]2(2-) dianion.

The hydrolysis of [ClP(mu-NtBu)]2 with H2O-Et3N in thf, followed by in situ lithiation with nBuLi gives the Li13 cage [[[O-P(mu-NtBu)]2Li2]3(LiCl)6Li(Cl/OnBu)0.5(thf)7], containing a [O-P(mu-NtBu)]2(2-) dianion that is isoelectronic with ligands of the type [(RN)P(mu-NR)]2(2-).