The reaction of R2P–P(SiMe3)Li (R = tBu, iPr) with the diimido molybdenum complex [(ArN)2MoCl2·dme] (Ar = 2,6‐iPr2C6H3; dme = 1,2‐dimethoxyethane) yielded the side‐on‐coordinated phosphanylphosphinidene anionic complexes [(2,6‐iPr2C6H3N)2Mo(Cl)(η2‐P=PR2)]– (7Mo, 8Mo). The thermal decomposition of [(2,6‐iPr2C6H3N)2M(Cl)(η2‐P=PR2)]– [M = Mo (7Mo), W (8W)] to [(2,6‐iPr2C6H3N)2M(Cl)(1,2‐η‐tBu2P=P–PtBu2)] [M = Mo (3Mo), W (3W)] was investigated by 31P{1H} NMR spectroscopy. The reactions of [(ArN)2MCl2·dme] (Ar = 2,6‐iPr2C6H3; M = Mo, W) with tBu2P–P(Li)–PtBu2 gave molybdenum and tungsten complexes [(2,6‐iPr2C6H3N)2M(Cl)(1,2‐η‐tBu2P=P–PtBu2)] (3Mo, 3W) bearing an unusual triphosphorus ligand. The solid‐state structures of [(2,6‐iPr2C6H3N)2Mo(Cl)(η2‐P=PtBu2)]– (7Mo), [(2,6‐iPr2C6H3N)2Mo(Cl)(η2‐P=PiPr2)]– (8Mo), [(2,6‐iPr2C6H3N)2Mo(Cl)(1,2‐η‐tBu2P=P–PtBu2)] (3Mo) and [(2,6‐iPr2C6H3N)2W(Cl)(1,2‐η‐tBu2P=P–PtBu2)] (3W) were established by single‐crystal X‐ray diffraction analysis.

A series of monomeric amino- and aryl(diphosphino)boranes has been synthesized and structurally characterized.

Reactions of (Et(2)N)(2)P-P(SiMe(3))Li with [Cp(2)MCl(2)] (M = Zr, Hf) in toluene or pentane yield the related terminal phosphanylphosphido complexes [Cp(2)M(Cl){η(1)-(Me(3)Si)P-P(NEt(2))(2)}]. The solid state structure of [Cp(2)Hf(Cl){η(1)-(Me(3)Si)P-P(NEt(2))(2)}] was established by single crystal X-ray diffraction. The reaction of (Et(2)N)(2)P-P(SiMe(3))Li with [Cp(2)ZrCl(2)] in THF or DME solutions leads to the formation of deep red crystals of the first neutral diamagnetic zirconocene-phosphanylphosphinidene dimer [Cp(2)Zr{μ(2)-P-P(NEt(2))(2)}(2)ZrCp(2)]. The molecular structure of this compound was confirmed by X-ray diffraction. The reactions of (R(2)N)(2)P-P(SiMe(3))Li with [CpZrCl(3)] yield the related tetraphosphetanes R(2)NP(μ(2)-PSiMe(3))(2)PNR(2), which apparently are formed as a result of a transfer of NR(2) groups from a P atom to the Zr atom.

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