Versatile binding modes of acyclic N2X2 (X = O, S and P) ligands towards [GeCl]+ and AuCl units

Maurya, Devesh; Karmakar, Joy; Sahoo, Padmini; Raut, Ravindra K.; Majumdar, Moumita

doi:10.1016/j.ica.2019.119380

Cited by 8 publications

(5 citation statements)

References 42 publications

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“…Light yellow 5 crystallized in the P 1̅ space group and features two distinct Ge atoms, a three-coordinated Ge(II) cation and a GeCl 3 – anion (Figure ). The structural metrics of 5 are similar to those of the related iminopyridine stabilized chlorogermyliumylidene complexes. − However, while the ionic complex reported by Jambor could be readily obtained from the reaction of the methoxy-functionalized iminopyridine and GeCl 2 , no detectable 5 could be achieved from mixing the α-iminopyridine ligand and the Ge(II) precursor (Figure S23).…”

Section: Resultssupporting

confidence: 59%

A Non-innocent Ligand Supported Germylene and Its Diverse Reactions

2020

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To expand the reactivity scope of divalent germanium, an α-iminopyridine supported dicoordinate germanium complex (2) was prepared from deamination of the corresponding pyridine-coordinated diamido germylene (1). The non-innocent ligand supported germanium compound can be viewed as a benzo-fused N-heterocyclic germylene or a neutral α-iminopyridine-coordinated germylone. While the Ge-ligand cooperation observed in the reaction of 2 with HCl and BCl3 confirms the presence of a vacant p orbital at the Ge(II) atom, the readily transferring of a ligand from 2 to MCl2 (M = Ge, Sn) with the extrusion of metallic germanium reflects the electron richness of the central Ge(0) atom. The germylone character of 2 was further verified via four-electron oxidation with 2 equiv of tetra-chloro-o-benzoquinone to give the corresponding six-coordinated germanium(IV) adduct.

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Section: Resultssupporting

confidence: 59%

A Non-innocent Ligand Supported Germylene and Its Diverse Reactions

2020

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“…The L1 stabilized stannyliumylidenes 9 and 1 0 (Scheme 6A) have been obtained using similar method and have been structurally characterized [27] . We have also reported the stabilization of the chlorogermyliumylidene within bis(imine) based ligands having furyl or thienyl groups ( L2 and L3 respectively) as their appendages (compounds 11 and 12 in Scheme 6B) [30] . In all these bis(imine) based tetradentate ligand stabilized chlorogermyliumylidenes 7, 8, 11, 12 , the heteroatoms in the appendages do not play role in the stabilization of the Ge(II) cationic sites.…”

Section: Introductionmentioning

confidence: 94%

“…[27] We have also reported the stabilization of the chlorogermyliumylidene within bis(imine) based ligands having furyl or thienyl groups (L2 and L3 respectively) as their appendages (compounds 11 and 12 in Scheme 6B). [30] In all these bis(imine) based tetradentate ligand stabilized chlorogermyliumylidenes 7, 8, 11, 12, the heteroatoms in the…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Chemistry of the Bis(imine)‐Based Tetradentate Ligand Stabilized Group 14 E(II) Cations (E=Ge and Sn)

Biswas

Patel

Deb

et al. 2022

The Chemical Record

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The ambiphilic Ge(II) and Sn(II) cationic species have been reported to be isolated through kinetic or thermodynamic stabilizations. Nonetheless, steric congestion or excessive coordination of donor atoms to the cationic center concurrently disfavors its prompt reactivity. Our research in this field revolves around the utilization of structurally non-rigid bis(imine) based tetradentate supporting ligands for the stabilization of Ge(II) and Sn(II) cationic species. Such E(II) cationic systems have been advantaged due to inherent flexibility present at the ligand backbone allowing disposal of E(II) orbitals through geometric rearrangements for further reactivity. The bifunctionality present in the ligand enables the first examples of Ge(II) bismonocations. Furthermore, the redox-active nature of the ligand encourages participation in chemical transformations. In this personal account we have provided a detailed discussion of our published work in this direction in the last five years.

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“…106 Majumdar and co-workers reported acyclic exible diiminodi(furan) and diiminodi(thiophene) ligands in which the two imino nitrogen coordinating sites can stabilise the chloro-germyliumylidene ion 67. 107 Another type of germyliumylidene stabilisation is the use of monoanionic ligands that form cyclic compounds, such as the aminotroponiminate derivatives 68a,b utilised by Dias et al in 1997, 34 and, more recently, by the group of Nagendran in 2019. 49 Power et al used a Dipp-substituted b-diketiminate ligand to form the two-coordinated germyliumylidene 69a.…”

Section: Chemical Science Reviewmentioning

confidence: 99%

“… 106 Majumdar and co-workers reported acyclic flexible diiminodi(furan) and diiminodi(thiophene) ligands in which the two imino nitrogen coordinating sites can stabilise the chloro-germyliumylidene ion 67. 107 …”

Section: Germyliumylidenesmentioning

confidence: 99%