Abstract
The structure of the title complex, [Cr2Rh2(C10H9)2(CO)9], was solved by single-crystal X-ray diffraction analysis in the P21/c space group. The crystal shows two units of the tetrametallic complex in the asymmetric unit. The most remarkable features of this new compound are the asymmetric bonding of the RhIII atom to the indenyl ligand, which can be formulated in terms of an η2;η3 coordination rather than η5, and the Rh—Rh distances of 2.6756 (6) and 2.6737 (6) Å that are characteristic of an intermetallic interaction supported by a bridging carbonyl ligand. The infrared spectroscopic signature informs of its clear bridging feature characterized by a significantly elongated C=O bond length compared to those in the two Rh-bound `terminal' carbonyl ligands.
Highlights
The structure of the title complex, [Cr2Rh2(C10H9)2(CO)9], was solved by singlecrystal X-ray diffraction analysis in the P21/c space group
In the course of our investigations we have focused on the use of the anion derived from tricarbonyl(6:2-methylindene)chromium, i.e 1 (Fig. 1)
The reason for the formal oxidation of Rh in this reaction is not clear, this new compound arises from the loss of one carbonyl ligand at the Rh atom and the establishment of an Rh—Rh interaction supported by a bridging CO ligand (Fig. 1), which according to FT–IR data is characterized by a typical stretching mode at 1712 cmÀ1 that contrasts with those of terminal carbonyl ligands
Summary
Benzylic-type anions of tricarbonyl(6-indenyl)chromium complexes (Ceccon et al, 1988) are known to behave as efficient ‘hemichelating’ (Werleet al., 2013) ligands of transition metal atoms such as PdII (Werleet al., 2013, 2016, 2017), PdI (Werleet al., 2015) and PtII (Werleet al., 2013). In the course of our investigations we have focused on the use of the anion derived from tricarbonyl(6:2-methylindene)chromium, i.e 1 (Fig. 1) This ligand was applied to the coordination of the RhI atom with [L2RhX]2 dimers (Werleet al., 2014). The Rh atoms are bonded to the five-membered ring of the indenyl ligand in an anti fashion with respect to the Cr(CO) moiety in a distorted 5 way, better described as 2;3 owing to the significant difference of interatomic distances existing between Rh3 (or Rh4) and atoms C35 and C30 of 2.343 (5) and 2.398 (5) A [or C50 2.379 (5) and C45 2.410 (6) A ], and atoms C36, C37, C38 [or C51 with C51—Rh4 = 2.217 (5), C52 with C52—Rh4 = 2.262 (5), C53 with C53—Rh4 = 2.240 (5) A ] of 2.202 (5), 2.258 (5) and 2.263 (5) A , respectively. The solution of the anion was transferred after 30 min at À40C via cannula transfer to an ether solution (5 ml)
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