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Our investigations on the ligand properties of stanna-closo-dodecaborate [SnB11H11]2- [1]

established a novel coordination mode. [1] was previously reported to serve as

monodentated ligand by use of the electron lonepair at the Sn-atom, whereas the second

electron remains located in the closo-sphere. From the reaction of [1][Bu3NMe] with

RuCl2(PPh3)n (n = 3 or 4) the binuclear complex [Ru(PPh3)2(SnB11H11)]2 was isolated in

crystalline form. The crystal structure confirms the coordination of one [SnB11H11]2- ligand

to the Ru(II)-center. In addition three B-H-Ru-bonds are formed. Its formation illustrates for

the first time that the stannaborate-cluster may stabilize coordinative unsaturated metal

complex fragments as fourdentated ligand. From the reaction of RuCl3-hydrate, PPh3 and

[1][Bu3NH] single crystals of the monoanionic Ru(III)-complex [Ru(PPh3)2(SnB11H11)2]-

were obtained in low yields. In this compound the stannaborate ligand serves as

fourdentated ligand. In addition a Sn-B-bond to a second ligand is formed. On the basis of

the Ru(II)nitrosyl complex K2[Ru(NO)Cl5] it was demonstrated, that a successive substitution

of the chloro-ligands through [1] is possible. IR-spectroscopic studies of

Ru(NO)Cl4(SnB11H11)]3- and [Ru(NO)Cl3(SnB11H11)2]4- confirm that [1] behaves in Ru(II)

complexes as a stonger sigma-donor ligand than Cl- and SnCl3-. The reaction of

[(hapto-C5H5)Ru(PPh3)2Cl] with [1][Bu3NH] proceeds under substitution of the halide and

subsequent formation of [(hapto-C5H5)Ru(PPh3)2(SnB11H11)]-. The reactivity of

RhCl(PPh3)3 with [SnB11H11]2- was studied in different solvents and stochiometric

amounts. Unfortunately only mixture of several complexes are formed, whose isolation

remained unsuccessfully. A one pot reaction of RhCl(PPh3)3, [1][Bu3NMe] and

2,5-norbornadiene yields [(hapto-C7H8)Rh(PPh3)2(SnB11H11)]-, wich was characterized by

single crystals X-ray diffraction. The reaction of [(hapto-C8H12)RhCl]2 or

[(hapto-C7H8)RhCl]2 with 6 [1] leads to the formation of [(hapto-C8H12)Rh(SnB11H11)3]5-

and [(hapto-C7H8)Rh(SnB11H11)3]5-, respectively.

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