Synthesis of a Manganese Germavinylidene Complex from Bis(germavinylidene)

Leung, Wing‐Por; So, Cheuk‐Wai; Kan, Kwok‐Wai; Chan, Hoi‐Shan; Mak, Thomas C. W.

doi:10.1021/ic050969u

Cited by 26 publications

(26 citation statements)

References 29 publications

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“…Thus, complex [Ge(6a)] can act as a two-electron donor ligand (Ge lone pair) towards Ni, Pd, Au, Ag 172 Mn. 173 Being in low oxidation state, the Ge center can also be engaged in redox chemistry. Indeed it can oxidize chalcogens (E = S, Se, Te) to generate the bridging E 2species via the germaketene >C=Ge=E intermediate.…”

Section: Reactivitymentioning

confidence: 99%

Geminal Dianions Stabilized by Main Group Elements

2019

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This review is dedicated to the chemistry of stable and isolable species that bear two lone pairs at the same C center, i.e. geminal dianions, stabilized by main group elements. Three cases can thus be considered: the gem dilithio derivative, for which the two substituents at C are neutral, the ylidiide derivatives, for which one substituent is neutral while the other is charged, and finally the geminal bisylides, for which the two substituents are positively charged. In this review the syntheses and electronic structures of the geminal dianions are presented, followed by the studies dedicated to their reactivity toward organic substrates and finally to their coordination chemistry and applications. Reactivity of doubleylides towards organic compounds. 4.4. Coordination chemistry of double ylides to metallic species. 4.4.1. Coordination to Group 2 Metals. 4.4.2. Coordination to Actinides: Uranium Complexes 4.4.3. Coordination to Group 4 Metals: Zirconium Complexes 4.4.4. Coordination to Group 6 Metals: Tungsten Complexes 4.4.5. Coordination to Group 7 Metals: Manganese and Rhenium Complexes 4.4.6. Coordination to Group 8 Metals: Iron Complexes 4.4.7. Coordination to Group 9 Metals: Rhodium and Iridium Complexes 4.4.8. Coordination to Group 10 Metals 4.4.9. Coordination to Group 11 (Coinage) Metals 4.4.10. Coordination to Group 12 Metals 4.5. Reactivity of double ylides towards main group elements. 4.5.1. Group 13 4.5.2. Group 14 4.5.3. Group 15 4.5.4. Group 16 4.5.5. Group 17 4.6. Carbodicarbenes 4.6.1. Synthesis 4.6.2. Reactivity 4.6.3. Coordination chemistry 4.6.4. Reactivity with main group elements 5. Conclusion 6. Acknowledgements 7. References lengths in complexes [(7)Mg(THF)] 2 and [(14)Mg(THF) 3 ] at 2.156(5)Å and 2.113(4)Å resp. are as expectedly significantly shorter than the ones measured in the dimers [(6a)Mg] 2 and [(10)Mg] 2 at 2.225(2)Å (av.) and 2.267(3)Å (av.). Electronic structureThe question of the nature of the bond between the AE metal and C was addressed. Harder et al.performed a DFT study first on models of [(6a)Ca] 2 and [(6f)Ca] where H atoms were considered in place of the real phenyl groups at P and groups (SiMe 3 and Ar resp.) at N. 49 In the case of the monomeric complex [(6f)Ca], the solvent molecules were not taken into account. Not surprising in light of the difference of electronegativity of the elements, the charge at C varied between -1.623 (monomer) and -1.847 (dimer) whereas charge at Ca varied between +1.760 (monomer) and +1.821 (dimer). The Ca-C bond was thus described as highly ionic. The calculations with the full dimeric system were carried out, and a slightly reduced charge was calculated at C (-1.778). The NPA charges were also compared to the ones in neutral 6aH 2 and the [Ca(6aH) 2 ] complex. Expectedly the charge at C goes from -1.079 to -1.409 to -1.778 (in 6aH2, [Ca(6aH) 2 ], [Ca(6a)] 2 resp.). The charge at N also increases (-1.474 to -1.580 to -1.665 resp.) upon deprotonation at C. Conversely, the charge at P varies but to a small extent (+1.747 to +1.727 to +1.7...

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Section: Reactivitymentioning

confidence: 99%

Geminal Dianions Stabilized by Main Group Elements

2019

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“…[16,17] This ligand was attractive for our purposes, as it is known to form geminal dimetallic complexes of not only Li 2 , but also of Al 2 , [32] Pb 2 , [33] Sn 2 , [33] Cr 2 , [34] Zn 2 , [35] and Li/Rh. [36] In addition, this ligand has been shown to form stable "C=M" carbenes supported by single metal centers such as Pt, [37] Ti, [38] Zr, [21,39] Sm, [40] Hf, [41] Mo, [42] Ge, [43,44] Ca, [45] and Ba. [46] We recently reported in a preliminary communication the syntheses of [({Ph 2 PA C H T U N G T R E N N U N G (NSiMe 3 )} 2 CNa 2 ) 2 ], 3, and [({Ph 2 P-A C H T U N G T R E N N U N G (NSiMe 3 )} 2 CLiNa) 2 ], 4, the first examples of geminal organodimetallic compounds containing a heavy alkali metal to be structurally characterized.…”

Section: Introductionmentioning

confidence: 99%

Homo‐ and Heterodimetallic Geminal Dianions Derived from the Bis(phosphinimine) {Ph₂P(NSiMe₃)}₂CH₂ and the Alkali Metals Li, Na, and K

Hull¹,

Carmichael²,

Noll³

et al. 2008

Chemistry A European J

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The geminal organodimetallic complexes [({Ph2P(NSiMe3)}2C)2M4], where M4=Na4, 3; Li2Na2, 4; LiNa3, 5; Li2K2, 6; Na2K2, 7, and Na3K, 8, have been prepared through a variety of methods including direct or sequential deprotonation of the neutral ligand with strong bases (tBuLi, nBuNa, (Me3Si)2NNa, PhCH2K or (Me3Si)2NK), transmetalation of the homometallic derivatives (M4=Li4, 2 or Na4, 3) with tBuONa or tBuOK, and by cation exchange upon mixing the homometallic complexes in an arene solution. Complexes 3-8 have been characterized by single-crystal X-ray diffraction and are found to form a homologous series of dimeric structures in the solid-state, in accord with the previously reported structure of 2. Each complex is composed of a plane of four metals, M4, in which the ligands adopt capping positions to form distorted M4C2 octahedral cores. The metals in homometallic complexes 2 and 3 define an approximate square, whereas the heterometallic derivatives 4-8 have distinctly rhombic arrangements. The lighter metals in 4-8 interact strongly with the carbanions and the heavier metals are pushed towards the periphery of the structures. 1H, 13C, 7Li, 31P, and 29Si multinuclear NMR spectroscopic studies, cryoscopic measurements, and electrospray ionization-mass spectroscopic studies are consistent with the dimers being retained in solution. Dynamic solution behavior was discovered for Li2Na2 complex 4, in which all five possible tetrametallic derivatives Li4, Li3Na, Li2Na2, LiNa3 and Na4 coexist. Density functional theory (DFT) and natural bond order (NBO) calculations in association with natural population analyses (NPA) reveal significant differences in the electronic structures of the variously metalated dianions. The smaller cations are more effective in localizing the double negative charge on the carbanion (in the form of two lone pairs), leading to differences in the distribution of the electron density within the ligand backbones. In turn, a complex interplay of hyperconjugation, electrostatics and metal-ligand interactions is found to control the resulting electronic structures of the geminal organodimetallic complexes.

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“…16 The existence of a monomeric germavinylidene intermediate in solution was demonstrated in the synthesis of manganese-germavinylidene complex [(Me 3 SiN PPh 2 ) 2 C Ge → Mn(CO) 2 Cp] (Cp = η 5 -C 5 H 5 ). 17 We have also reported the synthesis of [(Me 3 SiN PPh 2 ) 2 {(cod)RhCl}CGeCl] (cod = 1,5-cyclooctadiene) from the 1,2-addition reaction of 1 with (cod)RhCl. 17 We anticipated that bisgermvinylidene 1 is a potential source of reactive monomeric germavinylidene 'Ge C(PPh 2 NSiMe 3 ) 2 ' intermediate by breaking the weak Ge-Ge interaction of 1 in solution.…”

Section: Introductionmentioning

confidence: 99%

“…17 We have also reported the synthesis of [(Me 3 SiN PPh 2 ) 2 {(cod)RhCl}CGeCl] (cod = 1,5-cyclooctadiene) from the 1,2-addition reaction of 1 with (cod)RhCl. 17 We anticipated that bisgermvinylidene 1 is a potential source of reactive monomeric germavinylidene 'Ge C(PPh 2 NSiMe 3 ) 2 ' intermediate by breaking the weak Ge-Ge interaction of 1 in solution. In this paper, we report the [2 + 2] cycloaddition reaction of germavinylidene with AdNCO (Ad = Adamantyl) showing the existence of the carbon-germanium double bond character in 1.…”

Section: Introductionmentioning

confidence: 99%