ABSTRACT
Several compounds with unique structural motifs that have already been known from organotin sulfide chemistry, but remained unprecedented in organotin selenide chemistry so far, have been synthesized. The reaction of [(R1 Sn)4 Se6 ] (R1 =CMe2 CH2 C(O)Me) with N2 H4 â H2 O/(SiMe3 )2 Se and PhN2 H3 /(SiMe3 )2 Se led to the formation of [{(R2 Sn)2 SnSe4 }2 (µ-Se)2 ] (1; R2 =CMe2 CH2 C(Me)NNH2 ) and [{(R3 Sn)2 SnSe4 }2 (µ-Se)2 ] (2; R3 =CMe2 CH2 C(Me)NNPhH)). The addition of ortho-phthalaldehyde to [(R2 Sn)4 Se6 ] yielded a cluster with intramolecular bridging of the organic groups, namely, [(R4 Sn2 )2 Se6 ] (3; R4 =(CMe2 CH2 C(Me)NNCH)2 C6 H4 ). The introduction of organic ligands with longer chains finally allowed the isolation of inorganic-organic capsules of the type [(µ-R)3 (Sn3 Se4 )2 ]X2 , with R=(CMe2 CH2 C(Me)NNHC(O))2 (CH2 )4 and X=[SnC3 ], Cl (4 a, b) or R=CMe2 CH2 C(Me)NNH)2 and X=[SnCl3 ] (5). The capsules enclose solvent molecules and/or anions as guests. All compounds were characterized by means of single-crystal X-ray diffraction studies, NMR spectroscopy, and mass spectrometry.
ABSTRACT
Double deboronation of 1,1'-bis(ortho-carborane) results in a mixture of racemic and meso diastereoisomers which are sources of the [7-(7'-7',8'-nido-C2B9H10)-7,8-nido-C2B9H10]4- tetraanion. Consistent with this, metalation of the mixture with {Ru(p-cymene)} affords the diastereoisomers α-[1-(8'-2'-(p-cymene)-2',1',8'-closo-RuC2B9H10)-3-(p-cymene)-3,1,2-closo-RuC2B9H10] (3α) and ß-[1-(8'-2'-(p-cymene)-2',1',8'-closo-RuC2B9H10)-3-(p-cymene)-3,1,2-closo-RuC2B9H10] (3ß) in which the primed cage has undergone a spontaneous 3',1',2' to 2',1',8'-RuC2B9 isomerisation. Analogous cobaltacarboranes α-[1-(8'-2'-Cp-2',1',8'-closo-CoC2B9H10)-3-Cp-3,1,2-closo-CoC2B9H10] (4α) and ß-[1-(8'-2'-Cp-2',1',8'-closo-CoC2B9H10)-3-Cp-3,1,2-closo-CoC2B9H10] (4ß) are formed by metalation with CoCl2/NaCp followed by oxidation, along with a small amount of the unique species [8-(8'-2'-Cp-2',1',8'-closo-CoC2B9H10)-2-Cp-2,1,8-closo-CoC2B9H10] (5) if the source of the tetraanion is [HNMe3]2[7-(7'-7',8'-nido-C2B9H11)-7,8-nido-C2B9H11]. Two-electron reduction and subsequent reoxidation of 4α and 4ß afford species indistinguishable from 5. The reaction between [Tl]2[1-(1'-3',1',2'-closo-TlC2B9H10)-3,1,2-closo-TlC2B9H10] and [CoCpI2(CO)] leads to the isolation of a further isomer of (CpCoC2B9H11)2, rac-[1-(1'-3'-Cp-3',1',2'-closo-CoC2B9H10)-3-Cp-3,1,2-closo-CoC2B9H10] (6), which displays intramolecular dihydrogen bonding. Thermolysis of 6 yields 4α, allowing a link to be established between the α and ß forms of 3 and 4 and racemic and meso forms of the [7-(7'-7',8'-nido-C2B9H10)-7,8-nido-C2B9H10]4- tetraanion, whilst reduction-oxidation of 6 again results in a product indistinguishable from 5.
