Thorium-phosphorus triamidoamine complexes containing Th-P single- and multiple-bond interactions.
Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phosphorus are known, reflecting a general paucity of synthetic methodologies and also problems associated with stabilising these linkages at the large thorium ion. Here we report structurally authenticated examples of a parent thorium(IV)-phosphanide (Th-PH2), a terminal thorium(IV)-phosphinidene (Th=PH), a parent dithorium(IV)-phosphinidiide (Th-P(H)-Th) and a discrete actinide-phosphido complex under ambient conditions (Th=P=Th). Although thorium is traditionally considered to have dominant 6d-orbital contributions to its bonding, contrasting to majority 5f-orbital character for uranium, computational analyses suggests that the bonding of thorium can be more nuanced, in terms of 5f- versus 6d-orbital composition and also significant involvement of the 7s-orbital and how this affects the balance of 5f- versus 6d-orbital bonding character.
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Elizabeth P
EP
Wildman
Institute of Inorganic Chemistry, University of Regensburg, Universitaets str.31, Regensburg 93053, Germany.
Gábor
G
Balázs
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Ashley J
AJ
Wooles
Institute of Inorganic Chemistry, University of Regensburg, Universitaets str.31, Regensburg 93053, Germany.
Manfred
M
Scheer
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Stephen T
ST
Liddle
Chemistry. 2000 Apr 3;6(7):1252-7
10785812
Acta Crystallogr B. 2002 Jun;58(Pt 3 Pt 1):380-8
12037359
Chem Commun (Camb). 2005 Jun 14;(22):2773-7
15928755
Science. 2005 Dec 23;310(5756):1941-3
16373571
Angew Chem Int Ed Engl. 2006 Apr 3;45(15):2389-92
16526001
Dalton Trans. 2006 Jun 7;(21):2501-16
16718334
J Am Chem Soc. 2006 Aug 16;128(32):10549-59
16895423
Chem Soc Rev. 2007 Feb;36(2):367-77
17264937
J Am Chem Soc. 2008 Apr 16;130(15):5272-85
18366174
Angew Chem Int Ed Engl. 2008;47(29):5366-70
18601262
J Am Chem Soc. 2008 Sep 17;130(37):12536-46
18715008
J Am Chem Soc. 2009 Jan 28;131(3):963-72
19154173
J Am Chem Soc. 2009 Sep 2;131(34):12125-36
19705913
Dalton Trans. 2010 Feb 7;39(5):1145-58
20104334
Dalton Trans. 2009 Nov 14;(42):9260-5
20449204
Angew Chem Int Ed Engl. 2011 Mar 1;50(10):2383-6
21351360
J Am Chem Soc. 2011 Apr 27;133(16):6162-5
21452878
J Am Chem Soc. 2011 May 11;133(18):6894-7
21488697
Inorg Chem. 2011 Jul 18;50(14):6500-8
21667978
J Am Chem Soc. 2011 Aug 24;133(33):13183-96
21793520
Dalton Trans. 2011 Oct 14;40(38):9662-4
21814698
Angew Chem Int Ed Engl. 2011 Nov 18;50(47):11227-9
21956885
J Am Chem Soc. 2012 Mar 14;134(10):4931-40
22324788
J Am Chem Soc. 2012 Mar 28;134(12):5586-97
22404133
J Am Chem Soc. 2012 Jun 20;134(24):10047-54
22621395
J Am Chem Soc. 2012 Jun 20;134(24):9876-8
22670799
Science. 2012 Aug 10;337(6095):717-20
22745250
J Am Chem Soc. 2012 Sep 19;134(37):15468-75
22920602
Chem Rev. 2013 Feb 13;113(2):1137-98
23130707
J Am Chem Soc. 2013 Feb 13;135(6):2279-90
23320417
Chem Commun (Camb). 2013 Apr 14;49(29):2956-73
23396581
J Am Chem Soc. 2013 Apr 10;135(14):5352-5
23521401
Nat Chem. 2013 Jun;5(6):482-8
23695629
J Am Chem Soc. 2013 Jul 24;135(29):10742-54
23837946
J Am Chem Soc. 2013 Aug 14;135(32):12101-11
23915030
J Am Chem Soc. 2014 Jan 8;136(1):96-9
24350685
Angew Chem Int Ed Engl. 2014 Apr 22;53(17):4484-8
24644135
J Am Chem Soc. 2014 Apr 16;136(15):5619-22
24697157
Angew Chem Int Ed Engl. 2014 Jun 23;53(26):6696-700
24842784
Angew Chem Int Ed Engl. 2014 Sep 22;53(39):10412-5
25079093
J Phys Chem A. 2015 Mar 19;119(11):2326-37
25162610
Nat Chem. 2014 Oct;6(10):919-26
25242488
Angew Chem Int Ed Engl. 2015 Jul 20;54(30):8604-41
26079536
Nat Chem. 2015 Jul;7(7):582-90
26100807
J Am Chem Soc. 2015 Aug 5;137(30):9583-6
26200434
J Am Chem Soc. 2015 Aug 26;137(33):10492-5
26244991
J Am Chem Soc. 2015 Dec 2;137(47):14846-9
26575219
J Am Chem Soc. 2016 Jan 27;138(3):814-25
26667146
Dalton Trans. 2016 Feb 14;45(6):2390-3
26758474
Dalton Trans. 2016 Jun 14;45(24):10042-9
27122120
Chem Sci. 2015 Jul 1;6(7):3891-3899
29218160
Chem Sci. 2016 May 1;7(5):3286-3297
29997821