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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.

Mn(i) PNP pincer hydride complexes were shown for the first time to catalyse the hydrogenation of CO2 to formate reaching quantitative yields and high TONs.

Reaction of the dimer [(η5-C5Me5)RhCl(μ2-Cl)]2 with 2 or 4 equiv of the water-soluble phosphine 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane (pta) affords [Rh(η5-C5Me5)(pta)Cl2] and [Rh(η5-C5Me5)(pta)2Cl]Cl, respectively. Both complexes have been characterized in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction, the latter as the chloride and BPh4 - salts. In addition, the rhodium(I) complexes [Rh(η5-C5Me5)(CO)(pta)] and [Rh(η5-C5H5)(pta)2] have been prepared from [Rh(η5-C5Me5)(CO)2] and [Rh(η5-C5H5)(PPh3)2], respectively, by reaction with pta. An in vitro evaluation of these compounds, together with [Os(η6-C10H14)(pta)Cl2] and the well-characterized antimetastasis drug [Ru(η6-C10H14)(pta)Cl2], RAPTA-C, was undertaken using HT29 colon carcinoma, A549 lung carcinoma, and T47D breast carcinoma cells. In the HT29 cell line, the two nearest congeners to [Ru(η6-C10H14)(pta)Cl2], viz., [Rh(η5-C5Me5)(pta)Cl2] and [Os(η6-C10H14)(pta)Cl2], demonstrated very similar cytotoxicity profiles. [Rh(η5-C5Me5)(pta)Cl2] proved significantly more cytotoxic in A549 cells and [Rh(η5-C5Me5)(pta)2Cl]Cl 3-fold more cytotoxic in T47D cells, both relative to RAPTA-C. These data suggest that the development of organometallic anticancer drugs based on the neighboring elements to ruthenium should not be overlooked.