Synthesis of (RSn)4X6 Adamantanes (X = O, S, Se) in Liquid Ammonia and in the Two-Phase System Liquid Ammonia/THF

Abstract

Keywords: Adamantane / Liquid ammonia / Oxygen / Sulfur and selenium / TinThe reactions of trisSnBr 3 (1) [tris = (Me 3 Si) 3 C] and nBuSnCl 3 pressure at room temperature results in the formation of (trisSn) 4 S 6 (3) and (trisSn) 4 Se 6 (4). nBuSnCl 3 reacts with Na 2 S with Na 2 X (X = O, S, Se) yield the heterocyclic adamantanes 2-6. The reaction of 1 with Na 2 O is carried out in liquid and Na 2 Se in liquid ammonia at -33°C under normal pressure to give (nBuSn) 4 S 6 (5) and (nBuSn) 4 Se 6 (6), ammonia under normal pressure at -78°C to give (trisSn) 4 O 6 (2). However, the reaction of 1 with Na 2 S and Na 2 Se under respectively.gives a singlet at δ ϭ 0.32 for the protons of the methyl

The Ate Complexes [M{C(SiMe3)3}(μ-SBu)2Li(THF)2] (M = Ge or Sn). The First Structural Characterization of Organometallic Ate Complexes of Group 14 Metals in Oxidation State II

“…The geometry of the Tsi group is as expected for the group attached to Ge or Sn . The Ge II −Tsi bond in 1 (2.096(5) Å) is similar in length to those in the Ge II compounds Ge(Tsi)CH(SiMe 3 ) 2 (2.067(4) Å) 33 or Ge(Tsi)(η 5 -C 5 H 5 ) (2.135(17) Å) 34 and significantly longer than Ge IV −Tsi bonds (1.94(1) −1.99(1) Å). ,− Likewise the Sn II −Tsi bond in 2 (2.295(3) Å) is similar in length to the Sn−C bonds in the Sn II compounds [Sn{C(SiMe 2 Ph) 3 }Cl] 2 (2.296(10) Å) and [Sn{C(SiMe 3 ) 2 (SiMe 2 OMe)}Cl] 2 14 (2.294(5) Å) and significantly longer than the Sn−C bonds in tris(triorganosilyl)methyl−Sn IV derivatives (2.120(11) to 2.191(11) Å). − …”

“…The geometry of the Tsi group is as expected for the group attached to Ge or Sn. 32 The Ge II -Tsi bond in 1 (2.096(5) Å) is similar in length to those in the Ge II compounds Ge(Tsi)CH(SiMe 3 ) 2 (2.067-(4) Å) 33 or Ge(Tsi)(η 5 -C 5 H 5 ) (2.135(17) Å) 34 [38][39][40][41][42][43] The structures, especially that of 1, show a striking resemblance to that of the recently reported tri(methylthiolato)aluminate 3, 44 if the nonbridging MeS group in the latter is regarded as occupying the site taken up by the lone pair in 1 and 2. Since the covalent radii of Ge (1.25 Å) and Al (1.22 Å) are not much different, comparison between 1 and 3 is especially interesting.…”

The Ate Complexes [M{C(SiMe3)3}(μ-SBu)2Li(THF)2] (M = Ge or Sn). The First Structural Characterization of Organometallic Ate Complexes of Group 14 Metals in Oxidation State II

“…The geometry of the Tsi group is as expected for the group attached to Ge or Sn . The Ge II −Tsi bond in 1 (2.096(5) Å) is similar in length to those in the Ge II compounds Ge(Tsi)CH(SiMe 3 ) 2 (2.067(4) Å) 33 or Ge(Tsi)(η 5 -C 5 H 5 ) (2.135(17) Å) 34 and significantly longer than Ge IV −Tsi bonds (1.94(1) −1.99(1) Å). ,− Likewise the Sn II −Tsi bond in 2 (2.295(3) Å) is similar in length to the Sn−C bonds in the Sn II compounds [Sn{C(SiMe 2 Ph) 3 }Cl] 2 (2.296(10) Å) and [Sn{C(SiMe 3 ) 2 (SiMe 2 OMe)}Cl] 2 14 (2.294(5) Å) and significantly longer than the Sn−C bonds in tris(triorganosilyl)methyl−Sn IV derivatives (2.120(11) to 2.191(11) Å). − …”

“…The geometry of the Tsi group is as expected for the group attached to Ge or Sn. 32 The Ge II -Tsi bond in 1 (2.096(5) Å) is similar in length to those in the Ge II compounds Ge(Tsi)CH(SiMe 3 ) 2 (2.067-(4) Å) 33 or Ge(Tsi)(η 5 -C 5 H 5 ) (2.135(17) Å) 34 [38][39][40][41][42][43] The structures, especially that of 1, show a striking resemblance to that of the recently reported tri(methylthiolato)aluminate 3, 44 if the nonbridging MeS group in the latter is regarded as occupying the site taken up by the lone pair in 1 and 2. Since the covalent radii of Ge (1.25 Å) and Al (1.22 Å) are not much different, comparison between 1 and 3 is especially interesting.…”

Controlling the White‐Light Generation of [(RSn)4E6]: Effects of Substituent and Chalcogenide Variation

“…The selenide cluster 3 is isostructural to its lighter homologue. The Sn−Se bond lengths are 2.5227(9)–2.5292(10) Å long, thus longer as in 2 and in the expected range for organotinselenides . The variation in bond angles is slightly greater than in 2 , ranging from 100.82(5) to 117.13(3)°.…”

MeSi(CH2SnRO)3 (R=Ph, Me3SiCH2): Building Blocks for Triangular‐Shaped Diorganotin Oxide Macrocycles

“…Just to mention a few options out of many, the variation of the substituents R and/or replacing the CH 3 group with other substituents, the variation of the spacing between the silicon and tin centres as well as replacement of the MeSi bridgehead moiety with MeGe or with isoelectronic P, P=E (E=O, S, Se) or PM (M=transition metal moiety such as W(CO) 5 and others) might give a plethora of novel diorganotin oxides showing polynuclear structures. Moreover, replacing the organic substituent R in Roesky's (RSn) 4 O 6 ( R=(Me 3 Si) 2 CH) [3] by a R′ of slightly reduced steric bulk could give well defined oligomers [(R′Sn) 4 O 6 ] n similar to 7 and 8 .…”

The Ate Complexes [M{C(SiMe3)3}(μ-SBu)2Li(THF)2] (M = Ge or Sn). The First Structural Characterization of Organometallic Ate Complexes of Group 14 Metals in Oxidation State II

“…The geometry of the Tsi group is as expected for the group attached to Ge or Sn . The Ge II −Tsi bond in 1 (2.096(5) Å) is similar in length to those in the Ge II compounds Ge(Tsi)CH(SiMe 3 ) 2 (2.067(4) Å) 33 or Ge(Tsi)(η 5 -C 5 H 5 ) (2.135(17) Å) 34 and significantly longer than Ge IV −Tsi bonds (1.94(1) −1.99(1) Å). ,− Likewise the Sn II −Tsi bond in 2 (2.295(3) Å) is similar in length to the Sn−C bonds in the Sn II compounds [Sn{C(SiMe 2 Ph) 3 }Cl] 2 (2.296(10) Å) and [Sn{C(SiMe 3 ) 2 (SiMe 2 OMe)}Cl] 2 14 (2.294(5) Å) and significantly longer than the Sn−C bonds in tris(triorganosilyl)methyl−Sn IV derivatives (2.120(11) to 2.191(11) Å). − …”

“…The geometry of the Tsi group is as expected for the group attached to Ge or Sn. 32 The Ge II -Tsi bond in 1 (2.096(5) Å) is similar in length to those in the Ge II compounds Ge(Tsi)CH(SiMe 3 ) 2 (2.067-(4) Å) 33 or Ge(Tsi)(η 5 -C 5 H 5 ) (2.135(17) Å) 34 [38][39][40][41][42][43] The structures, especially that of 1, show a striking resemblance to that of the recently reported tri(methylthiolato)aluminate 3, 44 if the nonbridging MeS group in the latter is regarded as occupying the site taken up by the lone pair in 1 and 2. Since the covalent radii of Ge (1.25 Å) and Al (1.22 Å) are not much different, comparison between 1 and 3 is especially interesting.…”

Controlling the White‐Light Generation of [(RSn)4E6]: Effects of Substituent and Chalcogenide Variation

“…The selenide cluster 3 is isostructural to its lighter homologue. The Sn−Se bond lengths are 2.5227(9)–2.5292(10) Å long, thus longer as in 2 and in the expected range for organotinselenides . The variation in bond angles is slightly greater than in 2 , ranging from 100.82(5) to 117.13(3)°.…”

MeSi(CH2SnRO)3 (R=Ph, Me3SiCH2): Building Blocks for Triangular‐Shaped Diorganotin Oxide Macrocycles

“…Just to mention a few options out of many, the variation of the substituents R and/or replacing the CH 3 group with other substituents, the variation of the spacing between the silicon and tin centres as well as replacement of the MeSi bridgehead moiety with MeGe or with isoelectronic P, P=E (E=O, S, Se) or PM (M=transition metal moiety such as W(CO) 5 and others) might give a plethora of novel diorganotin oxides showing polynuclear structures. Moreover, replacing the organic substituent R in Roesky's (RSn) 4 O 6 ( R=(Me 3 Si) 2 CH) [3] by a R′ of slightly reduced steric bulk could give well defined oligomers [(R′Sn) 4 O 6 ] n similar to 7 and 8 .…”

The Ate Complexes [M{C(SiMe3)3}(μ-SBu)2Li(THF)2] (M = Ge or Sn). The First Structural Characterization of Organometallic Ate Complexes of Group 14 Metals in Oxidation State II

“…The geometry of the Tsi group is as expected for the group attached to Ge or Sn . The Ge II −Tsi bond in 1 (2.096(5) Å) is similar in length to those in the Ge II compounds Ge(Tsi)CH(SiMe 3 ) 2 (2.067(4) Å) 33 or Ge(Tsi)(η 5 -C 5 H 5 ) (2.135(17) Å) 34 and significantly longer than Ge IV −Tsi bonds (1.94(1) −1.99(1) Å). ,− Likewise the Sn II −Tsi bond in 2 (2.295(3) Å) is similar in length to the Sn−C bonds in the Sn II compounds [Sn{C(SiMe 2 Ph) 3 }Cl] 2 (2.296(10) Å) and [Sn{C(SiMe 3 ) 2 (SiMe 2 OMe)}Cl] 2 14 (2.294(5) Å) and significantly longer than the Sn−C bonds in tris(triorganosilyl)methyl−Sn IV derivatives (2.120(11) to 2.191(11) Å). − …”

“…The geometry of the Tsi group is as expected for the group attached to Ge or Sn. 32 The Ge II -Tsi bond in 1 (2.096(5) Å) is similar in length to those in the Ge II compounds Ge(Tsi)CH(SiMe 3 ) 2 (2.067-(4) Å) 33 or Ge(Tsi)(η 5 -C 5 H 5 ) (2.135(17) Å) 34 [38][39][40][41][42][43] The structures, especially that of 1, show a striking resemblance to that of the recently reported tri(methylthiolato)aluminate 3, 44 if the nonbridging MeS group in the latter is regarded as occupying the site taken up by the lone pair in 1 and 2. Since the covalent radii of Ge (1.25 Å) and Al (1.22 Å) are not much different, comparison between 1 and 3 is especially interesting.…”

Controlling the White‐Light Generation of [(RSn)4E6]: Effects of Substituent and Chalcogenide Variation

“…The selenide cluster 3 is isostructural to its lighter homologue. The Sn−Se bond lengths are 2.5227(9)–2.5292(10) Å long, thus longer as in 2 and in the expected range for organotinselenides . The variation in bond angles is slightly greater than in 2 , ranging from 100.82(5) to 117.13(3)°.…”

MeSi(CH2SnRO)3 (R=Ph, Me3SiCH2): Building Blocks for Triangular‐Shaped Diorganotin Oxide Macrocycles

“…Just to mention a few options out of many, the variation of the substituents R and/or replacing the CH 3 group with other substituents, the variation of the spacing between the silicon and tin centres as well as replacement of the MeSi bridgehead moiety with MeGe or with isoelectronic P, P=E (E=O, S, Se) or PM (M=transition metal moiety such as W(CO) 5 and others) might give a plethora of novel diorganotin oxides showing polynuclear structures. Moreover, replacing the organic substituent R in Roesky's (RSn) 4 O 6 ( R=(Me 3 Si) 2 CH) [3] by a R′ of slightly reduced steric bulk could give well defined oligomers [(R′Sn) 4 O 6 ] n similar to 7 and 8 .…”