Building upon previous studies on the synthesis of bis(sigma)borate and agostic complexes of ruthenium, the chemistry of nido-[(Cp Ru)2B3H9] (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 [Cp RuBH3L] (2a-c) and β-agostic complexes [Cp RuBH2L2] (3a-c; 2a, 3a: L=C7H4NS2; 2b, 3b: L=C7H4NSO; 2c, 3c: L=C7H5N2S). Further, the chemistry of these novel complexes towards various diphosphine ligands was investigated. Room temperature treatment of 3a with [PPh2(CH2)nPPh2] (n=1-3) yielded [Cp Ru(PPh2(CH2)nPPh2)-BH2(L2)] (4a-c; 4a: n=1; 4b: n=2; 4c: n=3; L=C7H4NS2). Mild thermolysis of 2a with [PPh2(CH2)nPPh2] (n=1-3) led to the isolation of [Cp Ru(PPh2(CH2)nPPh2)(L)] (L=C7H4NS2 5a-c; 5a: n=1; 5b: n=2; 5c: n=3). Treatment of 4a with terminal alkynes causes a hydroboration reaction to generate vinylborane complexes [Cp Ru(R-C=CH2)BH(L2)] (6 and 7; 6: R=Ph; 7: R=COOCH3; L=C7H4NS2). 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.