Remarkably Stable Chalcogen(II) Dications

Martin, Caleb D.; Le, Christine M.; Ragogna, Paul J.

doi:10.1021/ja9073968

Cited by 48 publications

(41 citation statements)

References 20 publications

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“…The CN double bonds in 3 are equal in length at 1.274(3) Å and are in good agreement with related main‐group complexes and also remain virtually unchanged compared with the uncomplexed ligand 54. 58, 59, 63…”

Section: Resultssupporting

confidence: 78%

“…In complex 1 , the N1C1 and N2C2 double‐bond lengths are 1.308(3) and 1.321(3) Å and are in the typical range for imino bond lengths of related complexes 54. 58, 59, 63 The observation of two distinctly different separations between the central low‐oxidation‐state main‐group center and the nitrogen donors of the imino groups, as seen in 1 (Sn1N1=2.397(2) Å, Sn1N2=2.315(2) Å, Sn1N3=2.122(2) Å), is also observed in several isoelectronic DIMPY‐based pnicogen(I) compounds [DIMPYPn I ] + . In [DIMPYP I ] + I 3 − , for example, the P I N(Dipp)C separations are 1.877(7) and 1.975(7) Å.…”

Section: Resultsmentioning

confidence: 89%

“…Related complexes with the same bonding motif as compound 1 , such as the cationic [DIMPYAs] + and [DIMPYTe] 2+ complexes, exhibit identical trends in the structural motifs with short N(pyr)E and longer (CN)E bonds 58. 59 As shown earlier, diiminopyridine ligands, which lack the opportunity to undergo enamine formation like DIMPY in PhDIMPY, cleanly react with pnicogen(I) centers (Pn I ) to give the respective cationic complexes DIMPY(Pn I ) + , which are isoelectronic to 1 and show similar bonding trends. In these complexes, the geometry of the ligand system is strictly constrained and similarly accounts for the trends in N(pyr)Pn I and (CN)Pn I separations.…”

Section: Resultsmentioning

confidence: 99%

“…Of these complexes, DIMPYSn ( 1 ) is of special interest because it features a complex in which the main‐group element center is in formal oxidation state zero, in contrast to Sn II complexes 2 to 4 . Neutral DIMPYSn complex 1 is isoelectronic to the above‐mentioned cationic Group 1558 (+I) and dicationic Group 1659 (+II) derivatives (Scheme ) and to the aryl‐based Sb I and Bi I compounds 64. In analogy, complex 1 would be the first example of a neutral, mononuclear complex of tin in a formal oxidation state of zero stabilized by one donor molecule.…”

Section: Introductionmentioning

confidence: 99%

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The Role of 2,6‐Diaminopyridine Ligands in the Isolation of an Unprecedented, Low‐Valent Tin Complex

Flock

Suljanovic

Torvisco

et al. 2013

Chemistry A European J

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Stabilization of the central atom in an oxidation state of zero through coordination of neutral ligands is a common bonding motif in transition-metal chemistry. However, the stabilization of main-group elements in an oxidation state of zero by neutral ligands is rare. Herein, we report that the transamination reaction of the DAMPY ligand system (DAMPY=2,6-[ArNH-CH2 ]2 (NC5 H3 ) (Ar=C6 H3 -2,6-iPr2 )) with Sn[N(SiMe3 )2 ]2 produces the DIMPYSn complex (DIMPY=(2,6-[ArNCH]2 (NC5 H3 )) with the Sn atom in a formal oxidation state of zero. This is the first example of a tin compound stabilized in a formal oxidation state of zero by only one donor molecule. Furthermore, three related low-valent Sn(II) complexes, including a [DIMPYSn(II) Cl](+) [SnCl3 ](-) ion pair, a bisstannylene DAMPY{Sn(II) [N(SiMe3 )2 ]2 }2 , and the enamine complex MeDIMPYSn(II) , were isolated. Experimental results and the conclusions drawn are also supported by theoretical studies at the density functional level of theory and (119) Sn Mössbauer spectroscopy.

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Section: Resultssupporting

confidence: 78%

Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The Role of 2,6‐Diaminopyridine Ligands in the Isolation of an Unprecedented, Low‐Valent Tin Complex

Flock

Suljanovic

Torvisco

et al. 2013

Chemistry A European J

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“…Di(imino)pyridine, die als erfolgreiche Liganden für Übergangsmetalle bekannt sind, ermöglichten es nun erstmals, hoch stabile Chalkogen(II)kationen zu isolieren. Die Verbindungen (25) sind über mehrere Wochen (Se) oder sogar Monate (S, Te) luftstabil und zersetzen sich selbst nach Zugabe von Wasser nicht 1_57…”

Section: Donor‐akzeptor‐stabilisierte Hauptgruppenverbindungenunclassified

Anorganische Chemie 2009

Baumgartner¹,

Pietschnig²,

Schatzschneider³

et al. 2010

Nachr Chem

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Molekülchemie der Hauptgruppenelemente: Trends wie die Donorstabilisierung niedervalenter Zentren oder allgemein Donor‐Akzeptor‐Synergien wurden weiter entwickelt. Bioanorganik: Neben den Forschungsfeldern der Metalloenzyme und des Metalloprotein‐Engineerings war die medizinische anorganische Chemie sehr dynamisch. Koordinationschemie: Artifizielle Systeme, die Methan in Methanol umwandeln, stehen möglicherweise am Beginn einer rasanten Entwicklung.

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Positively Charged Selenium‐ and Tellurium‐Stabilized Species

Sato

2014

Patai's Chemistry of Functional Groups

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Cationic chalcogenium species have attracted some attention due to the ability of these highly electropositive centers to interact with organic molecules or to provide strong π‐accepter ligands for transition metals. Though the cationic selenium and tellurium species are very useful for organic synthesis, most of the naked cationic chalcogen species, with the exception of tricoordinated chalcogenium salt (R 3 Ch + , Ch = chalcogen atoms), are unstable and difficult to isolate as a result of their intrinsic high reactivity. However, if the cationic chalcogen species are supported by the coordination of neighboring p ‐block elements bearing a lone electron pair, they are often stabilized dramatically. Several cationic selenium and tellurium species which are naturally unstable have been synthesized and isolated by the intra‐ and intermolecular coordination of various ligands. The main purpose of this chapter is to introduce the recent progress of positively charged selenium and tellurium species, mainly focused on the dicationic selenium(II, IV, VI) and tellurium(II, IV, VI) species, which are stabilized by the coordination with p ‐block elements.

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Remarkably Stable Chalcogen(II) Dications

Cited by 48 publications

References 20 publications

The Role of 2,6‐Diaminopyridine Ligands in the Isolation of an Unprecedented, Low‐Valent Tin Complex

The Role of 2,6‐Diaminopyridine Ligands in the Isolation of an Unprecedented, Low‐Valent Tin Complex

Anorganische Chemie 2009

Positively Charged Selenium‐ and Tellurium‐Stabilized Species

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