Document Type : Research Article

Authors

Department of Chemistry, Rani Channamma University, NH-4, Vidyasangama, Belagavi 596156, India

Abstract

In this work, we report the synthesis, structural characterization of Group 4 mono and bis-hydroxides and their derivatives and their catalytic properties in the Ring Opening Polymerization (ROP) of rac-Lactide. The hydroxides, and their multimetallic assemblies were characterized, using 1H NMR, 2D NMR, Elemental Analysis, and Single crystal XRD. These complexes were used as catalysts for ring opening polymerization of rac-Lactide.  All complexes exhibit varied activity in the polymerization but produce heterotactic polylactide in high yield. These polymers were further characterized by 13C NMR.
A tendency toward formation of heterotactic polylactide was observed in the bulk polymerizations. Copyright © 2017 VBRI Press.
 

Keywords

1.(a) Stephan, D. W.; Coord. Chem. Rev.,1989, 95, 41.
DOI:10.1002/(SICI)1521-3765(19980615)4:6<1100::AID-
CHEM1100>3.0.CO;2
-6
(b) Alt, H. G.; Koeppl, A.; Chem.
Rev.,2000, 100, 1205.
DOI:10.1021/cr9804700
(c)Abramo, G. P.; Li, L.; Marks, T. J.; J. Am.
Chem. Soc.,2002,
124
, 13966.
DOI: 10.1021/ja020870b

2.
(a) Komon, Z. J. A.; Bu, X.; Bazan, G. C.; J. Am. Chem. Soc.,
2000
, 122, 1830.
DOI:10.1021/ja994222c
(b)Komon, Z. J. A.; Bu, X.; Bazan, G. C.; J. Am.
Chem. Soc.,
2000
, 122, 12379.
DOI:10.1021/ja002042t
(c) raunstein, . ose, . n Comprehensive rganometallic
Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.;
Pergamon Press: Oxford, 1995; Vol. 10.

(d) raunstein, . ose, . n Catalysis by i-and Polynuclear
Metal Cluster Complexes; Adams, R. D., Cotton, F. A., Eds.;
Wiley-VCH: New York, 1998

3.(a) Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F.; Angew. Chem.,
Int. Ed. Engl., 1999, 38, 428.

DOI:10.1002/(SICI)1521-3773(19990215)38:4<428::AID-
ANIE428>3.0.CO;2
-3
(b) McKnight, A. L.; Waymouth, R. M.; Chem. Rev., 1998, 98,
2587.

DOI:10.1021/cr940442r
4.(a) Gurubasavaraj, P. M.; Mandal, S. W.; Roesky, H. W.; Oswald,
R. B.; Pal, A.; Noltemeyer, M.; Inorg. Chem.,2007, 46, 1056.

DOI:10.1021/ic060538r

(b) Gurubasavaraj, P. M.; Roesky, H. W.; Nekouelsharaki, B.; Pal,
A.; Herbst-Irmer, R.; Inorg. Chem., 2008, 47, 5324.

DOI:10.1021/ic800198e
(c)Gurubasavaraj, P. M.; Roesky, H. W.; J. Org. Inorg.Chem,
2015
, 1, 1.
DOI:10.21767/2472-1123.100005.
5.(a) Capshew, C. E. Eur. Pat. Ap 1. 7425, 1980 (Philips Petroleum
Co.)

DOI:10.1039/CC9960001923
(b) Sinn, H.;Kaminsk, W.Adu.; Organomet.
Chem., 1980, 18, 99.
DOI:10.1016/S0065-3055(08)60307-X
(c) Caulton K. G.; Hubert-Pfalzgra, L. G.; Chem. Rev., 1990. 90.
969.

DOI:10.1021/cr00104a003
6.
Volpin, M. E.; J.Organomet. Chem., 1980, 200,319.
DOI:10.1016/S0022-328X(00)88653-2

7.(a) Roesky,H.W.; Haiduc, I.; Hosmane, N.S.; Chem. Rev., 2003,
103, 2579.

DOI:10.1021/cr9020376q
(b) Rau, M. S.; Kretz, C. M.; Geoffroy, G. L.; Rheingold, A. L.;
Haggerty, B. S.; Organometallics, 1994, 13, 1624

DOI:10.1021/om00017a020
8.Delferro, M.; Marks, T. J.; Chem. Rev., 2011, 111, 2450.

DOI:10.1021/cr1003634
9.(a) Nakamura, A.; Ito, S.; Nozaki, K.; Chem. Rev., 2009, 109,
5215.

DOI:10.1021/cr900079r
(b) Chen, E. Y.-X.; Chem. Rev., 2009, 109, 5157.

DOI:10.1021/cr9000258.
10.(a) Maganas, D.; Trunschke, A.; Schlögl, R.; Neese, F.; Faraday
Discuss., 2016, 188, 181.

DOI:10.1039/C5FD00193E.
(b) Srivastav, S.; Kumar, V.; Gupta, R.; Cryst.
GrowthDes., 2016,
16
, 2874.
DOI:10.1021/acs.cgd.6b00176.
11.(a) Gurubasavaraj, P. M.; Roesky, H. W.; Veeresha Sharma P. M.;
Oswald, R. B.; Dolle, V.; Herbst-Irmer, R.; Pal, A.;
Organometallics.,2007, 26, 3346.

DOI:10.1021/om070235k
(b) Roesky, H. W.; Gurubasavaraj, P. M. U.S. Patent 8598284 B2,
2013.


(c) S. K. Mandal.; P. M. Gurubasavaraj.; H. W. Roesky.; R. B.
Oswald.; J. Magull and A. Ringe.; Inorg. Chem., 2007, 46, 7594.

DOI:10.1021/ic701063v
(d) S. K. Mandal.; P. M. Gurubasavaraj.; H. W. Roesky.; G.
Schwab.; D. Stalke.; R. B. Oswald and V. Dolle.; Inorg. Chem.,
2007, 46, 10158.

DOI:10.1021/ic7011765
12.
(a) Hillhouse,G. L.; Bercaw,J. E.; J. Am. Chem. Soc. 1984,
106
,5472.
DOI:10.1021/ic7011765
13.
Voronkov, M. G.; Dyakov, V. M.; Kirpichenko, S. V.; J.
Organomet.
Chem.,1982, 233, l.
DOI:10.1016/S0022-328X(00)86939-9
14.
(a) Verkade, J. G.; Acc. Chem. Res.,1993, 26, 483.
DOI: 10.1021/ar00033a005
(b) Verkade, J. G.; Cood.
Chem. Rev.,1994, 137, 233.
DOI:10.1016/0010-8545(94)03007-D
15.Kasperczyk, J. E.; Macromolecules., 1995, 28, 3937.

DOI:10.1021/ma00115a028
16.
DIRDIF94: Beurskens, P. T.; Admiraal, G.; Beurskens, G.;
Bosman, W. P.; de Delder, R.; Israel, R.; Smits, J. M. M. (1994).

The DIRDIF94 program system, Technical report of

crystallography laboratory, University of Nijmegen, Netherlands.

17.(a) CrystalStructure 3.6.0: Crystal Structure Analysis Package,
Rigaku and Rigaku/MSC (2000-2004) 9009 New Trails Dr. The
Woodlands TX 77381 USA.

(b) CRYSTALS Issue 10: Watkin, D.J., Prout, C.K. Carruthers,
J.R. & Betteridge, P.W. Chemical Crystallography Laboratory,
Oxford, UK (1996).