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. 2022 Sep 26;61(39):e202208851.
doi: 10.1002/anie.202208851. Epub 2022 Aug 25.

Spontaneous Decomposition of an Extraordinarily Twisted and Trans-Bent Fully-Phosphanyl-Substituted Digermene to an Unusual GeI Cluster

Keith Izod  1 , Mo Liu  1 , Peter Evans  1 , Corinne Wills  2 , Casey M Dixon  2 , Paul G Waddell  2 , Michael R Probert  2
Affiliations

Spontaneous Decomposition of an Extraordinarily Twisted and Trans-Bent Fully-Phosphanyl-Substituted Digermene to an Unusual GeI Cluster

Keith Izod et al. Angew Chem Int Ed Engl. .

Abstract

Ditetrelenes R2 E=ER2 (E=Si, Ge, Sn, Pb) substituted by multiple N/P/O/S-donor groups are extremely rare due to their propensity to disaggregate into their tetrylene monomers R2 E. We report the synthesis of the first fully phosphanyl-substituted digermene {(Mes)2 P}2 Ge=Ge{P(Mes)2 }2 (3, Mes=2,4,6-Me3 C6 H2 ), which adopts a highly unusual structure in the solid state, that is both strongly trans-bent and highly twisted. Variable-temperature 31 P{1 H} NMR spectroscopy suggests that 3 persists in solution, but is subject to a dynamic equilibrium between two conformations, which have different geometries about the Ge=Ge bond (twisted/non-twisted) due to a difference in the nature of their π-stacking interactions. Compound 3 undergoes unprecedented, spontaneous decomposition in solution to give a unique GeI cluster {(Mes)2 P}4 Ge4 ⋅5 CyMe (7).

Keywords: Cluster; Germanium; Multiple Bond; Phosphorus; Solid-State Structure.

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Conflict of interest statement

The authors declare no financial conflicts of interest.

Figures

Figure 1
Figure 1
Typical conformations of ditetrelenes (E=Si, Ge, Sn, Pb) and definition of trans‐bending and twist angles in trans‐bent ditetrelenes.
Figure 2
Figure 2
Selected examples of disilenes and digermenes bearing multiple heteroatom substituents (other than Si).
Figure 3
Figure 3
Structures of diphosphatetrylenes (R2P)2E.
Scheme 1
Scheme 1
Synthesis of 3.
Figure 4
Figure 4
Molecular structure of one of the two independent molecules of 3 viewed a) perpendicular to, and b) along the Ge−Ge axis; H atoms and solvent of crystallization omitted for clarity. Selected bond lengths [Å] and angles [°] [values for the second independent molecule in the asymmetric unit in square brackets]: Ge(1)‐Ge(2) 2.4476(9) [Ge(3)‐Ge(4) 2.4701(9)], Ge(1)‐P(1) 2.3318(16) [Ge(3)‐P(5) 2.3371(18)], Ge(1)‐P(2) 2.3176(16) [Ge(3)‐P(6) 2.3540(17)], Ge(2)‐P(3) 2.3483(15) [Ge(4)‐P(7) 2.3619(18)], Ge(2)‐P(4) 2.3753(16) [Ge(4)‐P(8) 2.3428(15)], P(1)‐Ge(1)‐P(2) 104.54(5) [P(5)‐Ge(3)‐P(6) 98.35(6)], P(3)‐Ge(2)‐P(4) 95.58(5) [P(7)‐Ge(4)‐P(8) 96.78(4)].
Figure 5
Figure 5
Newman projections illustrating the different conformations of the E2P4 cores of 2 and 3.
Figure 6
Figure 6
The twisted, but non‐trans‐bent digermene 4 viewed perpendicular to (left) and along (right) the Ge−Ge direction.
Figure 7
Figure 7
Illustration of the different π‐stacking modes in 2 and 3 (Ar=Mes).
Figure 8
Figure 8
HOMO (left) and LUMO (right) of 3.
Figure 9
Figure 9
Variable‐temperature 31P{1H} NMR spectra of 3 in d 8‐toluene [*(Mes)2P−P(Mes)2 (6), # signals due to decomposition product 7 (see below)].
Scheme 2
Scheme 2
Possible dynamic equilibria for 3 in solution (Ar=Mes).
Figure 10
Figure 10
31P{1H} NMR spectra of a solution of 3 in toluene recorded at 20 h intervals.
Figure 11
Figure 11
Molecular structure of 7 with 40 % probability ellipsoids and with H atoms and disordered solvent of crystallization omitted for clarity. Selected bond lengths [Å]: Ge(1)⋅⋅⋅Ge(2) 2.9267(3), Ge(1)‐Ge(3) 2.5622(4), Ge(1)‐Ge(4) 2.5802(3), Ge(2)‐Ge(3) 2.5656(3), Ge(2)‐Ge(4) 2.5749(4), Ge(3)⋅⋅⋅Ge(4) 3.5767(1) Ge(1)‐P(1) 2.3617(6), Ge(1)‐P(4) 2.3982(6), Ge(2)‐P(2) 2.3534(6), Ge(2)‐P(4) 2.4088(6), Ge(3)‐P(3) 2.4816(6), Ge(4)‐P(3) 2.4662(6).
Figure 12
Figure 12
Comparison of the cores of 7 and 8.
Scheme 3
Scheme 3
Proposed decomposition of 3 into 7 (free energy changes in square brackets are given in kJ mol−1 [(u)B97D/6‐311G(2d,p)]).
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