Azo Complexes of Osmium(II): Preparation and Reactivity of Organic Azide and Hydrazine Derivatives Gabriele Albertin Stefano Antoniutti Laura Bonaldo Alessandra Botter Jesús Castro 10.1021/ic302483e.s002 https://acs.figshare.com/articles/journal_contribution/Azo_Complexes_of_Osmium_II_Preparation_and_Reactivity_of_Organic_Azide_and_Hydrazine_Derivatives/2433268 Mixed-ligand hydride complexes OsHCl­(CO)­(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>) [L = P­(OMe)<sub>3</sub>, P­(OEt)<sub>3</sub>] were prepared by allowing OsHCl­(CO)­(PPh<sub>3</sub>)<sub>3</sub> (<b>1</b>) to react with an excess of phosphite P­(OR)<sub>3</sub> in refluxing toluene. Dichloro compounds OsCl<sub>2</sub>(CO)­(PPh<sub>3</sub>)<sub>2</sub>L (<b>3</b>,<b> 4</b>) were also prepared by reacting <b>1</b>, <b>2</b> with HCl. Treatment of hydrides OsHCl­(CO)­(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>), first with triflic acid and then with an excess of RN<sub>3</sub> afforded organic azide complexes [OsCl­(η<sup>1</sup>-N<sub>3</sub>R)­(CO)­(PPh<sub>3</sub>)<sub>2</sub>L]­BPh<sub>4</sub> (<b>5</b>–<b>7</b>) [R = 4-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>, C<sub>6</sub>H<sub>5</sub>CH<sub>2</sub>, C<sub>6</sub>H<sub>5</sub>; L = P­(OEt)<sub>3</sub>]. Benzylazide complexes react in CH<sub>2</sub>Cl<sub>2</sub>/ethanol solution, leading to the imine derivative [OsCl­(CO)­{η<sup>1</sup>-NHC­(H)­C<sub>6</sub>H<sub>4</sub>-4-CH<sub>3</sub>}­(PPh<sub>3</sub>)<sub>2</sub>{P­(OEt)<sub>3</sub>}]­BPh<sub>4</sub> (<b>8b</b>). Hydrazine complexes [OsCl­(CO)­(RNHNH<sub>2</sub>)­(PPh<sub>3</sub>)<sub>2</sub>L]­BPh<sub>4</sub> (<b>9</b>–<b>11</b>) [R = H, CH<sub>3</sub>, C<sub>6</sub>H<sub>5</sub>; L = P­(OMe)<sub>3</sub>, P­(OEt)<sub>3</sub>] were prepared by allowing hydride species OsHCl­(CO)­(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>) to react first with triflic acid and then with an excess of hydrazine. Aryldiazene derivatives [OsCl­(CO)­(ArNNH)­(PPh<sub>3</sub>)<sub>2</sub>L]­BPh<sub>4</sub> (<b>12</b>,<b> 13</b>) were also prepared following two different methods: (i) by oxidizing arylhydrazine [OsCl­(C<sub>6</sub>H<sub>5</sub>NHNH<sub>2</sub>)­(CO)­(PPh<sub>3</sub>)<sub>2</sub>L]­BPh<sub>4</sub> (<b>11</b>) with Pb­(OAc)<sub>4</sub> in CH<sub>2</sub>Cl<sub>2</sub> at −30 °C; (ii) by allowing hydride species OsHCl­(CO)­(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>) to react with aryldiazonium cations ArN<sub>2</sub><sup>+</sup> (Ar = C<sub>6</sub>H<sub>5</sub>, 4-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>) in CH<sub>2</sub>Cl<sub>2</sub>. The complexes were characterized spectroscopically and by X-ray crystal structure determination of OsHCl­(CO)­(PPh<sub>3</sub>)<sub>2</sub>[P­(OEt)<sub>3</sub>] (<b>2b</b>) and [OsCl­{η<sup>1</sup>-NHC­(H)­C<sub>6</sub>H<sub>4</sub>-4-CH<sub>3</sub>}­(CO)­(PPh<sub>3</sub>)<sub>2</sub>{P­(OEt)<sub>3</sub>}]­BPh<sub>4</sub> (<b>8b</b>). 2013-03-18 00:00:00 hydride RN CH 2Cl solution 3C OsCl CH 2Cl OsHCl triflic acid 6H complex