Close packing and isostructuralism of analogous Ph3E-E'R3 compounds (R = Me, E, E' = silicon, germanium, tin; R = Ph, E, E' = silicon, germanium, tin, lead): crystal structure of 1,1,1-trimethyl-2,2,2-triphenyldigermane (Ph3Ge-GeMe3)

Pa̋rkányi, László; Kàlmán, Alajos; Sharma, Sneh; Nolen, Dena M.; Pannell, Keith H.

doi:10.1021/ic00079a033

Cited by 36 publications

(28 citation statements)

References 2 publications

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“…1 while selected bond distances and angles are collected in Table 1. The three sterically encumbering iso-propyl groups in 3 result in a Ge-Ge distance of 2.4637(7) Å , which is longer than the corresponding bond lengths in Me 3 GeGePh 3 (5, 2.418(1) Å ) [66], Et 3 GeGePh 3 (6, 2.4253(7) Å ) [60]. Bu n 3 GeGePh 3 (7, 2.4208(8) Å ) [60], and Ph 3 GeGePh 3 (2, 2.446(1) Å ) [32].…”

Section: Resultsmentioning

confidence: 87%

Hydrogermolysis reactions involving the α-germylated nitriles R3GeCH2CN (R=Ph, Pri, But) and germanium amides R3GeNMe2 (R=Pri, But) with Ph3GeH: Substituent-dependent reactivity and crystal structures of Pri3GeGePh3 and But3Ge[NHC(CH3)CHCN]

Amadoruge

DiPasquale

Rheingold

et al. 2008

Journal of Organometallic Chemistry

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Section: Resultsmentioning

confidence: 87%

Hydrogermolysis reactions involving the α-germylated nitriles R3GeCH2CN (R=Ph, Pri, But) and germanium amides R3GeNMe2 (R=Pri, But) with Ph3GeH: Substituent-dependent reactivity and crystal structures of Pri3GeGePh3 and But3Ge[NHC(CH3)CHCN]

Amadoruge

DiPasquale

Rheingold

et al. 2008

Journal of Organometallic Chemistry

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“…A comparison between the structural parameters of complexes 3c , 4a , 5a , and those of the parent oligogermanes 3 , 4 , and 5 , respectively (Table ), shows minimal differences, indicating a strong mutual influence of the Ge2, aryl and M(CO) 3 fragments in the molecule, where the acceptor properties of M(CO) 3 are counterbalanced by a Ge2 donation.…”

Section: Resultsmentioning

confidence: 99%

Aryl Oligogermanes as Ligands for Transition Metal Complexes

et al. 2018

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The ligand properties of a series of aryl oligogermanes R3Ge‐GeAr3, 3–7 [Me3Ge‐GePh3 (3), Me3Ge‐Ge(pTol)3 (4), Ph3Ge‐GePh3 (5), (C6F5)3Ge‐GePh3 (6), Ph3Ge‐GeMe2GePh3 (7)] for the synthesis of transition metal carbonyl complexes such as R3Ge‐GeAr2(R′C6H4‐η6)M(CO)3 (M = Cr, 3a–7a; M = Mo, 3b; M = W, 3c) were investigated. The target complexes were obtained in moderate yields using several different synthetic approaches. The physicochemical properties of these new derivatives were investigated by IR, UV/Vis, NMR spectroscopy, electrochemistry, and DFT calculations. The molecular structures of 3c, 4a, and 5a were studied by single‐crystal X‐ray diffraction analysis. A comparative analysis of donor and acceptor properties of aryl oligogermanes as ligands for transition metal carbonyl complexes is reported.

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“…Furthermore, this possible hypervalency could impact the potential morphotropic steps as originally described by Kitaigorodskii (1), and observed for simpler group 14 systems where only tetrahedral structures were possible. For example, the system Ph 4 E (E = Si (2), Ge (3), Sn (4), Pb (5)) has been analyzed with respect to such structural variations, and more recent studies by Párkányi et al (6) illustrated a morphotropic step occurring in the heteronuclear intra(inter)-group 14 bonding organometallic compounds (R 3 EE′R′R 2 ). In these systems the packing coefficient, defined as:…”

Section: Introductionmentioning

confidence: 99%

“…where Z is the number of molecules in the unit cell, V m is the volume of the molecule, and V is the unit cell volume, must be significantly decreased to change the packing motif and create a morphotropic step (6). Thus, 1-4 present an appealing series with which to study whether the size changes of the group 14 element would be sufficient to change the packing coefficient.…”

Section: Introductionmentioning

confidence: 99%

Lewis acidity of group 14 elements toward intramolecular sulfur in ortho-aryl-thioanisoles

Munguia¹,

Pavel²,

Kapoor³

et al. 2003

Can. J. Chem.

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The series of compounds (o-CH 3 SC 6 H 4 )CH 2 EPh 3 (E = Si (1), Ge (2), Sn (3), and Pb (4)) have been synthesized and characterized by NMR spectroscopy and by single crystal X-ray diffraction. Compounds 1 and 2 are isostructural with a triclinic crystal system and P-1 space group; however, morphotropic steps occur between Ge and Sn, and Sn and Pb. While the E-S distances in 1 and 2 are 3.985 and 3.974 Å, respectively,~100% of the sum of the respective van der Waals (vdW) radii, there is a notable distortion from tetrahedral geometry about E. Compound 3 is also triclinic with P-1 symmetry, but has two molecules in the unit cell that demonstrate a distorted tetrahedral geometry and intramolecular Sn-S distances of 3.699 and 3.829 Å, 88% and 91% of the sum of the vdW radii. Compound 4 has a Pb-S distance of 3.953 Å (91% of Σ vdW radii). The structure of the Grignard coupling product [o-(SCH 3 )C 6 H 4 CH 2 ] 2 is also reported.Résumé : On a réalisé la synthèse d'une série de composés de formule (o-CH 3 SC 6 H 4 )CH 2 EPh 3 dans lesquels E = Si (1), Ge (2), Sn (3) et Pb (4) et on les a caractérisés par spectroscopie RMN et par diffraction des rayons X par un cristal unique. Les composés 1 et 2 sont isostructuraux avec un système cristallin triclinique et un groupe d'espace P-1; toutefois, on notre des différences morphotropes entre le Ge et le Sn ainsi qu'entre le Sn et le Pb. Alors que les distances E-S dans les composés 1 et 2 sont respectivement de 3,985 et 3,974 Å, environ 100 % de la somme des rayons respectifs de van der Waals, on note une distorsion notable par rapport à la géométrie tétraédrique autour de E. Le composé 3 est aussi triclinique avec une symétrie P-1, mais la maille cristalline comporte deux molécules ce qui dé-montre la présence d'une géométrie tétraédrique déformée alors que les distances intramoléculaires Sn-S de 3,699 et 3,829 Å correspondent respectivement à 88 % et 91 % de la somme des rayons de van der Waals. Dans le composé 4, la distance Pb-S est de 3,593 Å (91 % de la somme des rayons de van der Waals). On a aussi déterminé la structure du produit de couplage de Grignard [o-(SCH 3 )C 6 H 4 CH 2 ] 2 .

show abstract

Close packing and isostructuralism of analogous Ph3E-E'R3 compounds (R = Me, E, E' = silicon, germanium, tin; R = Ph, E, E' = silicon, germanium, tin, lead): crystal structure of 1,1,1-trimethyl-2,2,2-triphenyldigermane (Ph3Ge-GeMe3)

Cited by 36 publications

References 2 publications

Hydrogermolysis reactions involving the α-germylated nitriles R3GeCH2CN (R=Ph, Pri, But) and germanium amides R3GeNMe2 (R=Pri, But) with Ph3GeH: Substituent-dependent reactivity and crystal structures of Pri3GeGePh3 and But3Ge[NHC(CH3)CHCN]

Hydrogermolysis reactions involving the α-germylated nitriles R3GeCH2CN (R=Ph, Pri, But) and germanium amides R3GeNMe2 (R=Pri, But) with Ph3GeH: Substituent-dependent reactivity and crystal structures of Pri3GeGePh3 and But3Ge[NHC(CH3)CHCN]

Aryl Oligogermanes as Ligands for Transition Metal Complexes

Lewis acidity of group 14 elements toward intramolecular sulfur in ortho-aryl-thioanisoles

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