Introduction 4178 2. Group 7 Metals 4180 2.1. Manganese 4180 2.2. Rhenium 4180 3. Group 8 Metals 4182 3.1. Iron 4182 3.1.1. Iron Complexes Containing P 4 and P n Ligands Resulting from the Degradation of the P 4 Tetrahedron (n < 4) 4182 3.1.2. Synthesis, Coordination Chemistry, and Reactivity of Pentaphosphaferrocene 4187 3.1.3. Polymers and Supramolecular Assemblies Based on the Pentaphosphaferrocene Building Block 4194 3.1.4. Polyphosphorus Ligands, P x (x > 5) 4197 3.2. Ruthenium 4197 3.3. Osmium 4201 4. Group 9 Metals 4202 4.1. Cobalt 4202 4.2. Rhodium 4215 4.3. Iridium 4220 5. Group 10 Metals 4222 5.1. Nickel 4222 5.2. Palladium 4227 5.3. Platinum 4227 6. Group 11 Metals 4229 6.1. Copper 4229 6.2. Silver 4230 6.3. Gold 4231 7. Abbreviations 4232 8. Acknowledgments 4232 9. References 4232 † This contribution is dedicated to our colleague and friend Prof. Piero Stoppioni on occasion of his 65th birthday and in recognition of his outstanding achievements in the field of white phosphorus activation. ‡ Note: In figures showing X-ray crystal structures, H atoms are generally omitted for clarity unless specified.

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The terminal rhenium(I) phosphaethynolate complex [Re(PCO)(CO)(2)(triphos)] has been prepared in a salt metathesis reaction from Na(OCP) and [Re(OTf)(CO)(2)(triphos)]. The analogous isocyanato complex [Re(NCO)(CO)(2)(triphos)] has been likewise prepared for comparison. The structure of both complexes was elucidated by X-ray diffraction studies. While the isocyanato complex is linear, the phosphaethynolate complex is strongly bent around the pnictogen center. Computations including natural bond orbital (NBO) theory, natural resonance theory (NRT), and natural population analysis (NPA) indicate that the isocyanato complex can be viewed as a classic Werner-type complex, that is, with an electrostatic interaction between the Re(I) and the NCO group. The phosphaethynolate complex [Re(P=C=O)(CO)(2)(triphos)] is best described as a metallaphosphaketene with a Re(I)-phosphorus bond of highly covalent character.

A series of cationic palladium complexes of general formula [Pd(Me)(MeCN)(N-N)][PF(6)] (N-N = (phen) 1 a, 4,7-dichloro-1,10-phenanthroline (4,7-Cl(2)-phen) 2 a, 4,7-diphenyl-1,10-phenanthroline (4,7-Ph(2)-phen) 3 a, 4-methyl-1,10-phenanthroline (4-Me-phen) 4 a, 4,7-dimethyl-1,10-phenanthroline (4,7-Me(2)-phen) 5 a, 5,5,6,6-tetrafluoro-5,6-dihydro-1,10-phenanthroline (F(4)-phen) 6 a, containing different substituted phenanthroline ligands, have been prepared from the corresponding neutral chloro derivatives [Pd(Me)(Cl)(N-N)], (1 b-6 b). The X-ray crystal structure of [Pd(Cl)(2)(4,7-Cl(2)-phen)] (2 b') was determined. DFT calculations show that the electron density on the metal is tuned by the substituents on the ligands. The catalytic behavior of complexes 1 a-6 a in the CO/styrene and CO/p-Me-styrene copolymerizations was studied in detail, showing that the generated catalysts are active for at least 90 h, yielding copolymers of high molecular weight. A firm correlation between the electron density on palladium on the one hand and the catalytic activity of the complexes and the molecular weight and the stereochemistry of the polyketones synthesized on the other hand has been established: the catalyst containing the F(4)-phen is thus far the most active among those tested, yielding the syndiotactic CO/styrene copolymer with a stereoregularity of 96 % (uu triad) and with an M(w) value of 1 000 000.

The stability of phosphorene is shown to be degraded by water. However, the presence of a small amount of water allows the synthesis of high‐quality material in liquid exfoliation of black phosphorus using dimethylsulfoxide as solvent. A phosphorus/water molar ratio between 1.5 and 14 maximizes the quality of the phosphorene flakes and their stability.

The solvothermal reaction of magnesium(II) salts with formic acid in N,N-dimethylformamide/H 2 O at 140 °C for 24 h afforded two different polymeric magnesium(II) formates, depending on the relative DMF/H 2 O content. A trigonal (space group R3 j c) anhydrous phase Mg(HCOO) 2 (HCOOH) ⊃ (CH 3 ) 2 NH (1) is formed under "dilute" conditions, while the orthorhombic (space group Pbca) dihydrate Mg(HCOO) 2 • 2H 2 O (2) is the main product when the water content is higher. When 2 is dehydrated at 300 °C and subsequently exposed to water vapors, a quasi-reversible phase transition was observed, leading to a different polymorph of the same species (2a, monoclinic, space group P2 1 /c). The process was entirely followed by X-ray powder diffraction (XRPD) at variable temperatures, and the same XRPD technique was used for structure solution and refinement of compound 2a. Finally, CO 2 adsorption isotherms at ambient temperature were recorded for (preactivated) 2, in order to test it as greenhouse gas storage material. A (promising) maximum value of 1.32 wt% CO 2 is stored under these conditions, but the plateau in the adsorption curve was not reached because of the higher carbon dioxide pressures required.

Nickel nanoparticles were dispersed on the surface of exfoliated black phosphorus and the resulting nanohybrid Ni/2DBP showed an improved stability with respect to pristine 2D BP when kept under ambient conditions in the dark. Ni/2DBP was applied as a catalyst in the semihydrogenation of phenylacetylene and exhibited high conversion and selectivity towards styrene. These features were preserved after recycling tests revealing the high stability of the nanohybrid.

The burgeoning interest in two-dimensional (2D) black phosphorus (bP) contributes to the expansion of its applications in numerous fields. In the present study, 2D bP is used as a support for homogeneously dispersed palladium nanoparticles directly grown on it by a wet chemical process. Electron energy loss spectroscopy–scanning transmission electron microscopy analysis evidences a strong interaction between palladium and P atoms of the bP nanosheets. A quantitative evaluation of this interaction comes from the X-ray absorption spectroscopy measurements that show a very short Pd–P distance of 2.26 Å, proving for the first time the existence of an unprecedented Pd–P coordination bond of a covalent nature. Additionally, the average Pd–P coordination number of about 1.7 reveals that bP acts as a polydentate phosphine ligand toward the surface of the Pd atoms of the nanoparticles, thus preventing their agglomeration and inferring with structural stability. These unique properties result in a superior performance in the catalytic hydrogenation of chloronitroarenes to chloroanilines, where a higher chemoselectivity in comparison to other heterogeneous catalyst based on palladium has been observed.