Reactions of (Ph)tBuP-P(SiMe3)Li·3THF with [(PNP)TiCl2] and [MeNacNacTiCl2·THF]. Synthesis of first PNP titanium(IV) complex with phosphanylphosphinidene ligand [(PNP)Ti(Cl){η2-P-P(Ph)tBu}]
Abstract
Lithium derivative of diphosphane (Ph)tBuP-P(SiMe3)Li (1) was isolated for the first time and investigated in reactions with β-diketiminate (MeNacnac− = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2C6H3) and PNP-pincer (PNP = N[2-PiPr2-4-methylphenyl]2) Ti(III) complexes. The β-diketiminate titanium(III) complex containing phosphanylphosphido ligand [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2) was prepared in reaction of [MeNacNacTiCl2·THF] with (Ph)tBuP-P(SiMe3)Li in toluene solution with good yield and purity. Respective titanium(IV) complex involving phosphanylphosphinidene ligand [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) was synthesized by oxidation of complex (2) with [iBu3PAgCl]4. Interestingly, an analogus PNP titanium(IV) complex [(PNP)Ti(Cl){ɳ2-P-P(Ph)tBu}] (4) was obtained in the reaction of [(PNP)TiCl2] with (Ph)tBuP-P(SiMe3)Li in toluene solution and 1 : 1 molar ratio instead of the expected titanium(III) complex with phosphanylphosphido ligand. Solid-state structures of (Ph)tBuP-P(SiMe3)Li·3THF (1), [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2), [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) and [(PNP)Ti(Cl){ɳ2-P-P(Ph)tBu}] (4) determined by single-crystal X-ray diffraction reveald that in all obtained complexes both, the phosphanylphosphinidene (Ph)tBuP-P and phosphanylphosphido (Ph)tBuP-P(SiMe3) ligands are bidently coordinated to the metal center.
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- artykuł w czasopiśmie wyróżnionym w JCR
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DALTON TRANSACTIONS
no. 29,
pages 1 - 11,
ISSN: 1477-9226 - Language:
- English
- Publication year:
- 2018
- Bibliographic description:
- Ziółkowska A., Szynkiewicz N., Wiśniewska A., Pikies J., Ponikiewski Ł.: Reactions of (Ph)tBuP-P(SiMe3)Li·3THF with [(PNP)TiCl2] and [MeNacNacTiCl2·THF]. Synthesis of first PNP titanium(IV) complex with phosphanylphosphinidene ligand [(PNP)Ti(Cl){η2-P-P(Ph)tBu}]// DALTON TRANSACTIONS. -Vol. 29, (2018), s.1-11
- DOI:
- Digital Object Identifier (open in new tab) 10.1039/c8dt01833b
- Bibliography: test
-
- Anal. Calcd for C 36 H 54 ClNP 4 Ti: C, 61.07;
- (5H form the (Ph)tBuPP moiety and 6 H form the PNP ligand), 2.613 (m, 2H, PCH(CH 3 ) 2 ), 2.20 (m, 2H, PCH(CH 3 ) 2 ), 2.16 (s, 3H, Ar-CH 3 ), 1.64 (d, J = 15.41 H, C(CH 3 ) 3 ), 1.55 (dd, 3H, J = 14.81 open in new tab
- Hz, J = 7.04 Hz, PCH(CH 3 ) 2 ), 1.38 (dd, 3H, J = 15.16 Hz, J = 6.97 open in new tab
- Hz, PCH(CH 3 ) 2 ), 1.11 (dd, 3H, J = 15.16 Hz, J = 6.97 Hz, PCH(CH 3 ) 2 ), 0.96 (dd, 3H, J = 11.74 Hz, J = 6.97, PCH(CH 3 ) 2 ).
- H} (298 K, C 6 D 6 ): δ = 147.03 (d, J = 20.54 Hz, Ar-CH), 135.54 (d, J = 15.22 Hz, Ar-C ipso ), 132.34 (s, Ar-CH), 130.26 (s, Ar-CH), 129.516 (s, Ar-C ipso ), 128.56 (s, Ar-C ipso ), 128.11 (dd, J = 13.64, J = 0.60 Hz, Ar-C ipso ), 127.88 (d, J = 24 Hz, Ar-CH), 122.96 (s, Ar-C ipso ), 116.88 (t, J = 1.76, Ar-CH), 34.07 (s, PC(CH 3 ) 3 ), 29.44 (d, J = 13.20 Hz, PC(CH 3 ) 3 ), 23.14 (d, J = 11.60 Hz, PCH(CH 3 ) 2 ), 22.36 (s, PC(CH 3 ) 2 ), 20.54 (s, Ar-CH 3 ), 20.13 (d, J = open in new tab
- Hz, PCH(CH 3 ) 2 ), 20.04 (d, J = 8.89 Hz, PCH(CH 3 ) 2 ), 18.89 (d, J = 9.83 Hz, PCH(CH 3 ) 2 ). 31 P{ 1 H} NMR (298 K, C 6 D 6 ): δ = 738.8 (broad d, J PP = 457.8 Hz, J PP = 11.4 Hz, P-P(Ph)tBu), 116.0 (broad dt J PP = 457.8 Hz, J PP = 13.6 Hz, P-P(Ph)tBu), 35.3 (broad d, J PP = 42.6, PNP), 29.8 (dd, J PP = 42.6, 13.6 Hz, PNP). open in new tab
- Minor diastereomer in the 1 H-NMR spectrum was observed near the strongest signals: 1 H-NMR (298 K, C 6 D 6 ): δ = 2.21 (s, 3H, Ar-CH 3 ), 1.66 (d, J = 15.47 H, C(CH 3 ) 3 ), 1.50 (dd, 3H, J = open in new tab
- Hz, J = 7.18 Hz, PCH(CH 3 ) 2 ), 1.42 (dd, 3H, J = 15.36 Hz, J = open in new tab
- Hz, PCH(CH 3 ) 2 ), 1.04 (dd, 3H, J = 15.11 Hz, J = 7.04 Hz, PCH(CH 3 ) 2 ), 0.94 (dd, 3H, J = 15.34 Hz, J = 6.88, PCH(CH 3 ) 2 ). In the 13 C-NMR spectrum the signals of major diasteromer were weak, the signals of minor distereoisomer were invisible. 31 P{ 1 H} NMR (298 K, C 6 D 6 ): δ = 764.68 (broad d, J PP = 457.8 Hz, P-P(Ph)tBu), 115.99 (broad d, J PP = 457.8 Hz, P-P(Ph)tBu), 36.43 (broad d, J PP = 40.4, 15.44 Hz, PNP), 30.29 (dd, J PP = 40.4, 11.58 open in new tab
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- We present the reactivity of [(PNP)TiCl 2 ] and [ Me NacNacTiCl 2 •THF] towards the lithium derivative of diphosphane (Ph)tBuP-P(SiMe 3 )Li•nTHF. open in new tab
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