Hydroboration of Alkynes with Zwitterionic Ruthenium-Borate Complexes: Novel Vinylborane Complexes.

Building upon previous studies on the synthesis of bis(sigma)borate and agostic complexes of ruthenium, the chemistry of nido-[(CpRu)2 B3 H9] (1) with other ligand systems was explored. In this regard, mild thermolysis of nido-1 with 2-mercaptobenzothiazole (2-mbzt), 2-mercaptobenzoxazole (2-mbzo) and 2-mercaptobenzimidazole (2-mbzi) ligands were performed which led to the isolation of bis(sigma)borate complexes [CpRuBH3 L] (2 a-c) and β-agostic complexes [CpRuBH2 L2] (3 a-c; 2 a, 3 a: L=C7 H4 NS2 ; 2 b, 3 b: L=C7 H4 NSO; 2 c, 3 c: L=C7 H5 N2 S). Further, the chemistry of these novel complexes towards various diphosphine ligands was investigated. Room temperature treatment of 3 a with [PPh2 (CH2 )n PPh2 ] (n=1-3) yielded [CpRu(PPh2 (CH2 )n PPh2 )-BH2 (L2)] (4 a-c; 4 a: n=1; 4 b: n=2; 4 c: n=3; L=C7 H4 NS2). Mild thermolysis of 2 a with [PPh2 (CH2)n PPh2 ] (n=1-3) led to the isolation of [CpRu(PPh2 (CH2)n PPh2 )(L)] (L=C7 H4 NS2 5 a-c; 5 a: n=1; 5 b: n=2; 5 c: n=3). Treatment of 4 a with terminal alkynes causes a hydroboration reaction to generate vinylborane complexes [CpRu(R-C=CH2 )BH(L2)] (6 and 7; 6: R=Ph; 7: R=COOCH3; L=C7 H4 NS2). Complexes 6 and 7 can also be viewed as η-alkene complexes of ruthenium that feature a dative bond to the ruthenium centre from the vinylinic double bond. In addition, DFT computations were performed to shed light on the bonding and electronic structures of the new compounds.