Neutral Mononuclear and Binuclear Hexacoordinate Silicon Complexes withSiO5C Skeletons

Abstract

Treatment of the silanes (EtO)3Si(CH2)2SCH2C(O)OSiMe3 and (EtO)3Si(CH2)3OSiMe3 with two molar equivalents of 1‐hydroxy‐2‐pyridone in acetonitrile yielded the neutral hexacoordinate silicon complexes bis[μ‐(3‐thiapentanoato(2−)‐C5,O′:C5′,O)]tetrakis[1‐oxopyridin‐2‐olato(1−)]disilicon(IV) (6) and bis[1‐oxopyridin‐2‐olato(1−)][propanolato(2−)‐C3,O]silicon(IV) (8), respectively. The compounds 6·2CH3CN and 8 were characterized by solid‐state 29Si VACP/MAS NMR spectroscopy, mass spectrometry (FAB MS), and single‐crystal X‐ray diffraction.

Synthesis and crystal structures of bis[1-oxopyridin-2-olato(1−)]bis(pentafluorophenyl)silicon(IV)–tetrahydrofuran–pentane (2/1/1), bis[1-oxopyridin-2-olato(1−)]bis( p -tolyl)silicon(IV), and dimesitylbis[1-oxopyridin-2-olato(1−)]silicon(IV)

“…There are five entries of hexacoordinate R 2 Si(OPO) 2 [R = Me, Et, iPr, Ph; R 2 = (CH 2 ) 3 ] complexes containing two bidentate OPO ligands (CSD refcodes NITSAM, NITSEQ, NITSOA, NISMIN, NITSUG, respectively; Kraft & Brennessel, 2014). Also reported with two bidentate OPO ligands are monoorgano neutral hexacoordinate complexes, RSi(OPO) 2 X (X = Cl, F; CSD refcodes ODEFIP, ODEFOV, ODEFUB, ODEHAJ, and ODEHEN), and cationic pentacoordinate complexes, [RSi(OPO) 2 ] + X À (X = Cl, trifluoromethanesulfonate; CSD refcodes ODEGAI, ODEGIQ, ODEGOW, and ODEGUC; Koch et al, 2017) CN and [O(CH 2 ) 3 ]Si(OPO) 2 (CSD refcodes UBUWET and UBUWIX, respectively; Tacke, Burschka et al, 2001). Monodentate OPO ligand complexes of any metal are limited to three organosilicon complexes: Me 3 Si(OPO), tBu 2 Si(� 1 -OPO)(� 2 -OPO), and Ph 3 Si(OPO)•Ph 3 Si(OH)•0.5C 5 H 12 (CSD refcodes NITROZ, NITSOA, and NITRIT, respectively; Kraft & Brennessel, 2014).…”

Synthesis and crystal structures of bis[1-oxopyridin-2-olato(1−)]bis(pentafluorophenyl)silicon(IV)–tetrahydrofuran–pentane (2/1/1), bis[1-oxopyridin-2-olato(1−)]bis( p -tolyl)silicon(IV), and dimesitylbis[1-oxopyridin-2-olato(1−)]silicon(IV)

“…There are five entries of hexacoordinate R 2 Si(OPO) 2 [R = Me, Et, iPr, Ph; R 2 = (CH 2 ) 3 ] complexes containing two bidentate OPO ligands (CSD refcodes NITSAM, NITSEQ, NITSOA, NISMIN, NITSUG, respectively; Kraft & Brennessel, 2014). Also reported with two bidentate OPO ligands are monoorgano neutral hexacoordinate complexes, RSi(OPO) 2 X (X = Cl, F; CSD refcodes ODEFIP, ODEFOV, ODEFUB, ODEHAJ, and ODEHEN), and cationic pentacoordinate complexes, [RSi(OPO) 2 ] + X À (X = Cl, trifluoromethanesulfonate; CSD refcodes ODEGAI, ODEGIQ, ODEGOW, and ODEGUC; Koch et al, 2017) CN and [O(CH 2 ) 3 ]Si(OPO) 2 (CSD refcodes UBUWET and UBUWIX, respectively; Tacke, Burschka et al, 2001). Monodentate OPO ligand complexes of any metal are limited to three organosilicon complexes: Me 3 Si(OPO), tBu 2 Si(� 1 -OPO)(� 2 -OPO), and Ph 3 Si(OPO)•Ph 3 Si(OH)•0.5C 5 H 12 (CSD refcodes NITROZ, NITSOA, and NITRIT, respectively; Kraft & Brennessel, 2014).…”

Bis(catecholato)silicates: Synthesis and Structural Data

“…[70] In the same vein, other original structures of bis(catecholato)silicates are reported in Scheme 18. For example, Holmes prepared 2,2'-biphenolate silicates in 1990 (Scheme 20A), [71] Tacke replaced the catechol ligand with a 1hydroxy-2-pyridone ligand allowing the formation of a hexacoordinate silicon compound (Scheme 20B), [72] and Spange published an interesting silicate bearing coumarin ligands (Scheme 20C). [73] Studies on the reactivity of such structures would be of particular interest.…”

Crystal structures of tris[1-oxopyridine-2-olato(1−)]silicon(IV) chloride chloroform-d1disolvate, tris[1-oxopyridine-2-olato(1−)]silicon(IV) chloride acetonitrile unquantified solvate, andfac-tris[1-oxopyridine-2-thiolato(1−)]silicon(IV) chloride chloroform-d1disolvate

“…The dihedral angles formed between the O 2 Si chelate and OPO ligands are also similar to those of QOXSIF (9.39, 3.08, and 2.41 ). Structures of monodentate organosilicon OPO complexes include Ph 3 Si(OPO)ÁPh 3 Si(OH)Á0.5n-pentane, Me 3 Si(OPO), and tBu 2 Si( 1 -OPO)( 2 -OPO) (respective CSD refcodes NITRIT, NITROZ, and NITSOA; Kraft & Brennessel, 2014), and of bidentate organosilicon OPO complexes include Ph 2 Si(OPO) 2 , Me 2 Si(OPO)Cl, Ph 3 Si(OPO), Me 2 Si(OPO) 2 , Et 2 Si(OPO) 2 , iPr 2 Si(OPO) 2 , tBu 2 Si( 1 -OPO)( 2 -OPO), and (CH 2 ) 3 Si(OPO) 2 (respective CSD refcodes NISMIN, NISMOT, NITRUF, NITSAM, NITSEQ, NITSOA, NITSIU, and NITSUG;Kraft & Brennessel, 2014), and [Si(OPO) 2 (-CH 2 CH 2 SCH 2 C( O)O)] 2 Á2CH 3 CN and [O(CH 2 ) 3 ]Si(OPO) 2 (respective CSD refcodes UBUWET and UBUWIX; Tacke, Burschka et al, 2001). (I) and (II) have 0.06-0.17 Å shorter Si-O bond lengths and 3-5 larger ligand bite angles than those in chelated R 2 Si(OPO) 2 (R = alkyl, phenyl) complexes, indicating a stronger chelate presumably due, in part, to their cationic character.…”

Synthesis and crystal structures of bis[1-oxopyridin-2-olato(1−)]bis(pentafluorophenyl)silicon(IV)–tetrahydrofuran–pentane (2/1/1), bis[1-oxopyridin-2-olato(1−)]bis( p -tolyl)silicon(IV), and dimesitylbis[1-oxopyridin-2-olato(1−)]silicon(IV)

“…There are five entries of hexacoordinate R 2 Si(OPO) 2 [R = Me, Et, iPr, Ph; R 2 = (CH 2 ) 3 ] complexes containing two bidentate OPO ligands (CSD refcodes NITSAM, NITSEQ, NITSOA, NISMIN, NITSUG, respectively; Kraft & Brennessel, 2014). Also reported with two bidentate OPO ligands are monoorgano neutral hexacoordinate complexes, RSi(OPO) 2 X (X = Cl, F; CSD refcodes ODEFIP, ODEFOV, ODEFUB, ODEHAJ, and ODEHEN), and cationic pentacoordinate complexes, [RSi(OPO) 2 ] + X À (X = Cl, trifluoromethanesulfonate; CSD refcodes ODEGAI, ODEGIQ, ODEGOW, and ODEGUC; Koch et al, 2017) CN and [O(CH 2 ) 3 ]Si(OPO) 2 (CSD refcodes UBUWET and UBUWIX, respectively; Tacke, Burschka et al, 2001). Monodentate OPO ligand complexes of any metal are limited to three organosilicon complexes: Me 3 Si(OPO), tBu 2 Si(� 1 -OPO)(� 2 -OPO), and Ph 3 Si(OPO)•Ph 3 Si(OH)•0.5C 5 H 12 (CSD refcodes NITROZ, NITSOA, and NITRIT, respectively; Kraft & Brennessel, 2014).…”

Bis(catecholato)silicates: Synthesis and Structural Data

“…[70] In the same vein, other original structures of bis(catecholato)silicates are reported in Scheme 18. For example, Holmes prepared 2,2'-biphenolate silicates in 1990 (Scheme 20A), [71] Tacke replaced the catechol ligand with a 1hydroxy-2-pyridone ligand allowing the formation of a hexacoordinate silicon compound (Scheme 20B), [72] and Spange published an interesting silicate bearing coumarin ligands (Scheme 20C). [73] Studies on the reactivity of such structures would be of particular interest.…”

Crystal structures of tris[1-oxopyridine-2-olato(1−)]silicon(IV) chloride chloroform-d1disolvate, tris[1-oxopyridine-2-olato(1−)]silicon(IV) chloride acetonitrile unquantified solvate, andfac-tris[1-oxopyridine-2-thiolato(1−)]silicon(IV) chloride chloroform-d1disolvate

“…The dihedral angles formed between the O 2 Si chelate and OPO ligands are also similar to those of QOXSIF (9.39, 3.08, and 2.41 ). Structures of monodentate organosilicon OPO complexes include Ph 3 Si(OPO)ÁPh 3 Si(OH)Á0.5n-pentane, Me 3 Si(OPO), and tBu 2 Si( 1 -OPO)( 2 -OPO) (respective CSD refcodes NITRIT, NITROZ, and NITSOA; Kraft & Brennessel, 2014), and of bidentate organosilicon OPO complexes include Ph 2 Si(OPO) 2 , Me 2 Si(OPO)Cl, Ph 3 Si(OPO), Me 2 Si(OPO) 2 , Et 2 Si(OPO) 2 , iPr 2 Si(OPO) 2 , tBu 2 Si( 1 -OPO)( 2 -OPO), and (CH 2 ) 3 Si(OPO) 2 (respective CSD refcodes NISMIN, NISMOT, NITRUF, NITSAM, NITSEQ, NITSOA, NITSIU, and NITSUG;Kraft & Brennessel, 2014), and [Si(OPO) 2 (-CH 2 CH 2 SCH 2 C( O)O)] 2 Á2CH 3 CN and [O(CH 2 ) 3 ]Si(OPO) 2 (respective CSD refcodes UBUWET and UBUWIX; Tacke, Burschka et al, 2001). (I) and (II) have 0.06-0.17 Å shorter Si-O bond lengths and 3-5 larger ligand bite angles than those in chelated R 2 Si(OPO) 2 (R = alkyl, phenyl) complexes, indicating a stronger chelate presumably due, in part, to their cationic character.…”

Synthesis and crystal structures of bis[1-oxopyridin-2-olato(1−)]bis(pentafluorophenyl)silicon(IV)–tetrahydrofuran–pentane (2/1/1), bis[1-oxopyridin-2-olato(1−)]bis( p -tolyl)silicon(IV), and dimesitylbis[1-oxopyridin-2-olato(1−)]silicon(IV)

“…There are five entries of hexacoordinate R 2 Si(OPO) 2 [R = Me, Et, iPr, Ph; R 2 = (CH 2 ) 3 ] complexes containing two bidentate OPO ligands (CSD refcodes NITSAM, NITSEQ, NITSOA, NISMIN, NITSUG, respectively; Kraft & Brennessel, 2014). Also reported with two bidentate OPO ligands are monoorgano neutral hexacoordinate complexes, RSi(OPO) 2 X (X = Cl, F; CSD refcodes ODEFIP, ODEFOV, ODEFUB, ODEHAJ, and ODEHEN), and cationic pentacoordinate complexes, [RSi(OPO) 2 ] + X À (X = Cl, trifluoromethanesulfonate; CSD refcodes ODEGAI, ODEGIQ, ODEGOW, and ODEGUC; Koch et al, 2017) CN and [O(CH 2 ) 3 ]Si(OPO) 2 (CSD refcodes UBUWET and UBUWIX, respectively; Tacke, Burschka et al, 2001). Monodentate OPO ligand complexes of any metal are limited to three organosilicon complexes: Me 3 Si(OPO), tBu 2 Si(� 1 -OPO)(� 2 -OPO), and Ph 3 Si(OPO)•Ph 3 Si(OH)•0.5C 5 H 12 (CSD refcodes NITROZ, NITSOA, and NITRIT, respectively; Kraft & Brennessel, 2014).…”

Bis(catecholato)silicates: Synthesis and Structural Data

“…[70] In the same vein, other original structures of bis(catecholato)silicates are reported in Scheme 18. For example, Holmes prepared 2,2'-biphenolate silicates in 1990 (Scheme 20A), [71] Tacke replaced the catechol ligand with a 1hydroxy-2-pyridone ligand allowing the formation of a hexacoordinate silicon compound (Scheme 20B), [72] and Spange published an interesting silicate bearing coumarin ligands (Scheme 20C). [73] Studies on the reactivity of such structures would be of particular interest.…”

Crystal structures of tris[1-oxopyridine-2-olato(1−)]silicon(IV) chloride chloroform-d1disolvate, tris[1-oxopyridine-2-olato(1−)]silicon(IV) chloride acetonitrile unquantified solvate, andfac-tris[1-oxopyridine-2-thiolato(1−)]silicon(IV) chloride chloroform-d1disolvate

“…The dihedral angles formed between the O 2 Si chelate and OPO ligands are also similar to those of QOXSIF (9.39, 3.08, and 2.41 ). Structures of monodentate organosilicon OPO complexes include Ph 3 Si(OPO)ÁPh 3 Si(OH)Á0.5n-pentane, Me 3 Si(OPO), and tBu 2 Si( 1 -OPO)( 2 -OPO) (respective CSD refcodes NITRIT, NITROZ, and NITSOA; Kraft & Brennessel, 2014), and of bidentate organosilicon OPO complexes include Ph 2 Si(OPO) 2 , Me 2 Si(OPO)Cl, Ph 3 Si(OPO), Me 2 Si(OPO) 2 , Et 2 Si(OPO) 2 , iPr 2 Si(OPO) 2 , tBu 2 Si( 1 -OPO)( 2 -OPO), and (CH 2 ) 3 Si(OPO) 2 (respective CSD refcodes NISMIN, NISMOT, NITRUF, NITSAM, NITSEQ, NITSOA, NITSIU, and NITSUG;Kraft & Brennessel, 2014), and [Si(OPO) 2 (-CH 2 CH 2 SCH 2 C( O)O)] 2 Á2CH 3 CN and [O(CH 2 ) 3 ]Si(OPO) 2 (respective CSD refcodes UBUWET and UBUWIX; Tacke, Burschka et al, 2001). (I) and (II) have 0.06-0.17 Å shorter Si-O bond lengths and 3-5 larger ligand bite angles than those in chelated R 2 Si(OPO) 2 (R = alkyl, phenyl) complexes, indicating a stronger chelate presumably due, in part, to their cationic character.…”