Ring Opening of Dilithio Bis(amido)cyclodiphosphazanes As a Route to 1,3-Diaza-2λ²-phosphaallyl Gallium Complexes

Abstract

Gallium trichloride reacted with [(tBuNP)2(tBuNLi·THF)2] or [(tBuNP)2(PhNLi·THF)2] to form {[(tBuNP)2(tBuN)2]GaCl}, 1, and {[(tBuNP)2(PhN)2]GaCl·THF}, 3, respectively. Treatment of either gallium complex with [(tBuNP)2(tBuNLi·THF)2] produced {[(tBuNP)2(RN)2]Ga(tBuNPNtBu)}, R = tBu (2), R = Ph (4), respectively. The complexes 1 and 2 were X-ray structurally characterized, and 2 was shown to contain a 1,3-diaza-2λ2-phosphaallyl ligand. Compound 1 has Cs symmetry and crystallizes with two molecules in a monoclinic unit cell, space group P21/m (No. 11), having dimensions (213 K) a = 9.5478(6) Å, b = 11.9540(7) Å, c = 97.808(1) Å, β = 97.808(1)°. The crystal data (213 K) for 2 are orthorhombic, space group Pnma (No. 62), a = 19.0514(2) Å, b = 17.5082(1) Å, c = 9.6695(1) Å, and Z = 4.

Synthesis and Derivatization of the Bis(amido)‐λ3‐cyclodiphosphazanes cis‐[R′(H)NP(μ‐NR)]2, Including a Rare Example, trans‐[tBu(H)N(Se)P(μ‐NCy)]2, Showing Intermolecular Se···H–O Hydrogen Bonding

“…The 31 P NMR spectrum of 3 exhibits a single resonance at δ = 93.8 ppm, which is in the range of that previously reported for the bis(amido)-λ 3 -cyclodiphosphazane derivatives. [14,15] The dichloro derivative 2 was readily converted into the bis-(amido) derivative 3 by treatment of 2 with four equivalents of cyclohexylamine in diethyl ether at 0°C. …”

“…The (15)(16)(17) in quantitative yield. All of the three compounds were air-stable, white crystalline solids.…”

“…The structure for cis- (15) with the atom numbering scheme is shown in Figure 6. The selected bond angles and bond lengths for 15 are presented in Table 2 www.eurjic.orgable with those of the reported [20] imine derivatives of λ 5 -cyclodiphosphazanes.…”

“…NtBu)] 2 (1a), [14] and cis-[Ph(H)NP(μ-NtBu)] 2 (1b) [15] were prepared according to the published procedures. PCl 3 , CyNH 2 , tBuNH 2 , H 2 O 2 (33% in H 2 O), sulfur, selenium, and N 3 P(O)(OPh) 2 were purchased from commercial sources and were purified prior to use by the conventional methods.…”

Syntheses and spectroscopic investigation of some cyclophosphazanes: Analysis of pseudo‐triplet splitting

“…The chemistry of small inorganic heterocycles of the type (P N) 2 researches [1][2][3], mainly because such molecules are good starting materials for polycyclic inorganic and organometallic compounds [4,5]. The wide range applications of cyclophosphazanes in nucleophilic substitution reactions on P Cl bonds [6,7], coordination chemistry [8], and ring-opening polymerization reactions [9] causes a significant attraction to this area of chemistry.…”