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Syntheses and single-crystal X-ray diffraction studies of heterobicyclic cyclodiphosphazanes having central phosphorus(III) and arsenic(III) atoms are described. Interaction of PCl3 or AsCl3 with cis-[(tBuNP)2(tBuNLixTHF)2] produced the isomorphous ([(tBuNP)2(tBuN)2]ECl); E = P(1), As(4), respectively. These Cs-symmetric molecules crystallize with two molecules in the monoclinic space group P2(1)/m. Unit cell dimensions of 1 are (293 K) a = 9.777(1) A, b = 11.745(1) A, c = 9.986(2) A, and beta = 97.44(1) degrees; those of 4 are (213 K) a = 9.688(3) A, b = 11.873(3) A, c = 9.975(3) A, and beta = 97.80(3) degrees. When ([(tBuNP)2(tBuN)2]PCl) was treated with NaN3 or LiN(SiMe3)2, ([(tBuNP)2(tBuN)2]PN3)(2) and ([(tBuNP)2(tBuN)2]PN(SiMe3)2)(3), respectively, were obtained. Compound 2 crystallizes in the monoclinic space group P2(1)/m and has until-cell dimensions (213 K) of a = 9496(7) A, b = 12455(7) A, c = 10043(6) A, and beta = 9723(4) degrees, Z = 2.

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The interaction of (MeSiN(t)Bu)(2)(N(t)BuLi)(2) with MCl(4) in hot toluene produces {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MCl(2,) M = Zr (1), Hf (2), in good yields. The light-yellow and colorless solids are isostructural and crystallize in the monoclinic crystal system, space group P2(1)/n, with four molecules in the unit cell. The unit cell dimensions for 1 (293 K) are a = 9.174(6) Å, b = 18.027(13) Å, c = 16.515 Å, beta = 98.81(6) degrees, and those for 2 (213 K) are a = 9.1871(1) Å, b = 17.8553(2) Å, c = 16.4770(3) Å, beta = 99.339(1) degrees. The metal atoms are pseudotetrahedrally coordinated by cyclodisilazane and chloride ligands but have one additional weak bonding interaction with a cyclodisilazane ring-nitrogen atom. Treatment of 1 or 2 with 2 equiv of MeMgCl in ether affords the corresponding dimethyl species {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MMe(2), M = Zr (3), Hf (4). These isostructural, colorless organometallic compounds are remarkably stable to atmospheric oxygen and moisture. They crystallize in the monoclinic space group C2/c, Z = 4. The cell parameters for 3 (298 K) are a = 18.867(2) Å, b = 9.361(1) Å, c = 18.059(3) Å, beta = 119.49(1) degrees, and those for 4 (212 K) are a = 18.8066(4) Å, b = 9.3208(2) Å, c = 17.8725(3) Å, beta = 119.508(1) degrees. The dimethyl species are structurally very similar to the dichloro complexes 1 and 2, with the notable exception that the metal centers in these organometallic compounds are truly four-coordinate.

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