Platinum Complexes Bearing a Tripodal Germyl Ligand

Abstract

The reaction of the germane [Ge(H)(2-C 6 H 4 PPh 2 ) 3 ] (1) and the platinum precursor complex [Pt(nbe) 3 ] (nbe = norbornene) gave a racemic mixture of the germyl complex [Pt(nor){Ge(2-C 6 H 4 PPh 2 ) 3 }] (2; nor = exo-2-norbornyl, exo-2-bicyclo[2.2.1]heptyl). Mechanistic studies showed that the hydrido complex [Pt(H){Ge(2-C 6 H 4 PPh 2 ) 3 }] (3) is not formed as an intermediate during the formation of 2. Further studies revealed [a]

Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear PtII→GeIV Complex

“…It is also worth pointing out that complex B [7] (Figure 1) is the only other reported example of a light‐assisted bond formation between a main group element and a transition metal. The Ge‐Pt bond distance of 2.3338(4) Å in 2 is comparable to that found in [( o ‐dppp) 3 Ge]PtCl (2.3545(2) Å), a complex that has recently been described [14] . The Pt‐Cl (2.3891(8) Å) and Ge‐Cl (2.2088(10) Å) bonds are also notably longer than the corresponding linkages in 1 (average Pt‐Cl=2.34 Å; average Ge‐Cl=2.14 Å), in agreement with the more reduced nature of the dinuclear core of 2 .…”

“…TheG e-Pt bond distance of 2.3338(4) in 2 is comparable to that found in [(odppp) 3 Ge]PtCl (2.3545(2) ), ac omplex that has recently been described. [14] TheP t-Cl (2.3891( 8) )a nd Ge-Cl (2.2088( 10) )b onds are also notably longer than the corresponding linkages in 1 (average Pt-Cl = 2.34 ;average Ge-Cl = 2.14 ), in agreement with the more reduced nature of the dinuclear core of 2.While platinum complexes such as 2,w ith ortho-phenylene-based PGeP pincer ligands are absent from the literature, [15] we will note that related palladium complexes have been previously described and used as catalysts. [16] Given that recyclability is ad esirable feature of lightdriven catalytic schemes,w eb ecame eager to test whether 2 could be re-oxidized into 1.W ef irst attempted to carry out this oxidation using HCl.…”

Photoreductive Elimination of PhCl Across the Dinuclear Core of a [GePt]VI Complex

“…The same geometrical constraints affect the tetrahedral coordination geometry of the germanium atom as indicated by the larger than expected C6–Ge–C20 angle of 118.08(7)°. The Pt–Ge and Pt–Cl bond distances of 2.3572(5) and 2.3915(7) Å are similar to those of the previously reported complex 1 -Cl (2.3338(4) and 2.3891(8) Å, respectively), as well as the PGeP pincer complexes E and F (Figure ) reported by Cabeza (Pt–Ge distances 2.3017(5) Å and 2.3140(8) Å), , as well as that seen in [ClPtGe­( o -dppp) 3 ] ( G , Figure ) described by Braun (Ge–Pt distance = 2.3545(2) Å) …”

Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear PtII→GeIV Complex

“…TheG e-Pt bond distance of 2.3338(4) in 2 is comparable to that found in [(odppp) 3 Ge]PtCl (2.3545(2) ), ac omplex that has recently been described. [14] TheP t-Cl (2.3891( 8) )a nd Ge-Cl (2.2088( 10) )b onds are also notably longer than the corresponding linkages in 1 (average Pt-Cl = 2.34 ;average Ge-Cl = 2.14 ), in agreement with the more reduced nature of the dinuclear core of 2.While platinum complexes such as 2,w ith ortho-phenylene-based PGeP pincer ligands are absent from the literature, [15] we will note that related palladium complexes have been previously described and used as catalysts. [16] Given that recyclability is ad esirable feature of lightdriven catalytic schemes,w eb ecame eager to test whether 2 could be re-oxidized into 1.W ef irst attempted to carry out this oxidation using HCl.…”