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INORGANIC HYDRIDES

Boranes, metalloboranes, Transition state hydrides

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INORGANIC HYDRIDES

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  1. INORGANIC HYDRIDES

  2. Carboranes:

  3. Types of Carboranes:

  4. Types of Carboranes:

  5. Types of Carboranes:

  6. Wade’s rule:

  7. Metalloboranes:

  8. Metallocarboranes: • Metallocarboranes or metallocarboboranes are metal complexes where carboranes or heteroboranes act as ligands with at least one metal atom incorporated in the cage framework • They are inorganic polyhedral clusters which contain carbon, boron, hydrogen and metal ion in different combinations. • A typical example of metallocarborane is the [C2B9H11]2- (dicarbollide) cluster having a metal atom sandwiched between two dicarbollide units. • Preparation of [C2B9H11]2- (dicarbollide) C2B10H12 + MeO- + 2MeOH → [C2B9H12]- + H2 + B(OMe)3 [C2B9H12]- + NaH → [C2B9H11]2- + H2 +Na+ • Preparation of metallocarboranes 2[C2B9H11]2- + FeCl2 → [(C2B9H11)2Fe]2- + 2Cl- [C2B9H11]2- + C5H5- + FeCl2 → [C2B9H11FeC5H5]- +2Cl- [C2B9H11]2- + BrMn(CO)5 → [C2B9H11Mn(CO)3]- + Br- + 2CO

  9. TRANSITION METAL HYDRIDES • Metal carbonyl hydrides are complexes of transition metals with carbonmonoxide andhydride as ligands • These complexes are useful in organic synthesis as catalyst in homogeneous catalysis, such as hydroformylation reaction • Synthesis:

  10. Iron tetracarbonyl dihydride – H2Fe(CO)4 • Iron tetracarbonyl dihydride is the first transition metal hydride metal hydride with the formula H2Fe(CO)4. This complex is stable at low temperatures but decomposes rapidly at temperatures above –20°C. • The iron tetracarbonyl hydride shows geometry intermediate between octahedral and tetrahedral geometry. • Viewed as an octahedral complex, the hydride ligands are cis. • Viewed as a tetrahedral Fe(CO)4 complex, the hydrides occupy adjacent faces of the tetrahedron.

  11. Cobalt tetracarbonyl hydride – HCo(CO)4 • Cobalt tetracarbonyl hydride is a transition metal hydride with the formula HCo(CO)4. • It is a volatile, yellow liquid that forms a colorless vapour and has an intolerable odour. • HCo(CO)4 adopts trigonal bipyrimidal structure with the equatorial CO ligands slightly bent out of the equatorial plane. • The hydride ligand occupies one of the axial positions. The Co–CO and Co–H bond distances were determined to be 1.764 and 1.556 Å, respectively.

  12. Pentacarbonyl hydridomanganese – HMn(CO)5 • Pentacarbonyl hydridomanganeseis a transition metal hydride with formula [HMn(CO)5]. • This compound is one of the most stable "first-row" transition metal hydride. • The compound has octahedral symmetry and the H-Mn bond length is 1.44 ± 0.03 Å

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