The study of the reaction of water with the first-row transition-metal ions is continued in this work. Here we report the study of the reaction of water with the middle (Cr+, Mn+, and Fe+) first-row transition-metal cations in both high- and low-spin states. In agreement with experimental observations, the oxides are predicted to be more reactive than the metal ions, and no exothermic products are observed. Formation of endothermic products is examined. An in-depth analysis of the reaction paths leading to the observed products is given, including various minima, and several important transition states. All results have been compared with existing experimental and theoretical data, and our earlier works covering the (Sc+, Ti+, V+) + H2O reactions to observe existent trends for the early first-row transition-metal ions. The MO+ + H2 energy relative to M+ + H2O increases through the series from left to right. Additionally, the Fe+ case is seen to be significantly different from the entire Sc+−Mn+ series because both its low- and high-spin cases involve paired electrons, and Mn+ shows some differences because of the complete half-filling of its valence shell in the high-spin case.

In this paper we conclude the study of the reaction of water with the first row transition metal ions. We report the study of the reaction of water with the late (Co+, Ni+, and Cu+) first row transition metal cations in both high- and low-spin states. In agreement with experimental observations, no exothermic products are found and the oxides are predicted to be more reactive than the metal ions. Formation of endothermic products is examined. An in-depth analysis of the reaction paths possible for these reactions is given, including various minima and several important transition states. All results have been compared with existing experimental and theoretical data, and our earlier works covering the (Sc+-Fe+) + H2O reactions to observe existent trends for the first row transition metal ions.

The study of the reaction of water with the early first-row transition metal ions has been completed in this work, in both high-and low-spin states. In agreement with experimental observations, the only exothermic products are the low-lying states MO + + H 2 ; formation of other endothermic products is also examine. An in-depth analysis of the reaction paths leading to each of the observed products is given, including various minima and several important transition states. All results have been compared with existing experimental data and our earlier work covering the Ti + + H 2 O reaction in order to observe existent trends for the early first-row transition metal ions.

The primary reaction of titanium-catalyzed oligomerization of phosphorus using methylphosphine as a reagent has been studied with a highly accurate quantum mechanical procedure. The reaction proceeds as a two-step process with the titanium atom catalyzing the migration of a hydrogen atom from carbon to phosphorus by delocalizing electrons into its unoccupied d orbitals. Thus in the transition state of the second step it has been clearly identified a two-electron three-center bond among titanium, the phosphorus, and the migrating hydrogen atom, which drives the hydrogen from the carbon over to the phosphorus.