The reaction of K[B(CN)4] with [Ph4P]Cl, [nBu4P]Br, [nBuPh3P]Br, or [EtPh3P]Cl (Ph = phenyl, nBu = n‐butyl, Et = ethyl) affords [Ph4P][B(CN)4] (1), [nBu4P][B(CN)4] (2), [EtPh3P][B(CN)4] (3), and [nBuPh3P][B(CN)4] (4) in high yields. The structures of the compounds 1–3, which contain the tetrahedral [B(CN)4]– ion, were determined by single‐crystal X‐ray diffraction. 1 crystallizes in the tetragonal space group I\bar{4}2d (no. 122), a = 12.948(2), c = 29.382(6) Å, Z = 8, R1(F)/wR2(F2) = 0.0335/0.0953; 2 and 3 with orthorhombic symmetry; 2: space group Pnna (no. 52), a = 18.2187(6), b = 12.0707(3), c = 11.6704(4) Å, Z = 4, R1(F)/wR2(F2) = 0.0489/0.1532; 3: space group Pnma (no. 62), a = 14.1777(3), b = 13.4214(3), c = 12.3199(2) Å, Z = 4, R1(F)/wR2(F2) = 0.0477/0.1505. The IR, Raman, and NMR spectra as well as thermal data derived from DSC and TGA measurements are reported. Depending on the thermal stability of the phosphonium cation some of the tetracyanidoborates are stable up to ~370 °C with the liquid state having a range of up to 300 K. Such salts could be very useful as weakly coordinating reaction media.

A new synthetic pathway for the preparation of benzoate-functionalized phosphanes for microwave-mediated traceless Staudinger ligations is described. Novel phosphane derivatives based on 4-substituted iodophenyl benzoates were prepared via palladium(II)-catalyzed P-C cross-coupling reaction strategy in high yields. The application of microwave conditions for the ligation reactions reduced the reaction time considerably. An approach to fast and facile labeling strategies using this ligation was established.

Complete exchange: [M(6)X(12)] type cluster compounds with an octahedral M(6) metal atom arrangement, which is completely surrounded by alcoholato ligands, were unknown until now. The first representatives are prepared containing a [Nb(6)(OR)(12)](4+) unit (R = CH(3) or C(2)H(5)). They are accessible at elevated temperatures from strongly basic alcoholate solutions of [Nb(6)Cl(12)](2+)-containing precursors. C gray, H white, K turquoise, Nb blue, O red.

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Twisting the silicon backbone conformation in oxygen containing oligosilanes towards dihedral angles of 120-130 degrees either by intramolecular hydrogen bonding or incorporation into a covalently bonded ring system effectively extends the delocalization of electrons in these sigma-n mixed conjugated systems.