Synthesis and Structural Characterization of Thiophosphinoyl Late‐Transition‐Metal and Divalent Lanthanide Complexes Derived from 2‐Quinolyl‐Linked (Thiophosphorano)methane

Abstract

The synthesis and structural characterization of a series of late‐transition‐metal and divalent lanthanide complexes derived from 2‐quinolyl‐linked phosphoranosulfide CH2(iPr2P=S)(C9H6N‐2) are reported. Metathesis of dimeric lithium complex [(Li{Et2O}{CH(iPr2P–S)(C9H6N‐2)})2] (1) with CoCl2 (2 equiv.) afforded a heteroleptic cobalt(II) complex [(CoCl{CH(iPr2P=S)2(C9H6N‐2)})2] (2). Treatment of potassium complex [(K{CH(iPr2P–S)(C9H6N‐2)})n] (3) with MCl2 (M = Mn, Fe, Co; 1 equiv.) afforded homoleptic 2‐quinolyl‐linked (thiophosphorano)methanide metal(II) complexes, [M{CH(iPr2P–S)2(C9H6N‐2)}2] [M = Mn (4), Fe (5), Co (6)]. Metathesis reaction of 3 with [YbI2(thf)2] and [EuI2(thf)2] (1 equiv.) afforded dimeric homoleptic ytterbium(II) complex [(Yb{CH(iPr2P–S)(C9H6N‐2)}2)2] (7) and europium(II) complex [(Eu{CH(iPr2P–S)(C9H6N‐2)}2)2] (8), respectively. The structures of 2 and 4–8 have been determined by X‐ray crystallography. Furthermore, the magnetic susceptibility of compounds 4–6 have been determined by using Evan's method.

Inserted products of lithium silylquinolylamide dimers [{8-(2-R-C9H5N)N(Me3Si)}Li·OEt2]2 (R = H or Me) with dimethylcyanamide and their reactive derivatives with metal halides

“…23 In complex 4, the distances of the cobalt atom to quinolyl nitrogen atoms [Co1-N5 = 2.062(3) and Co2-N1 = 2.058(3) Å] are slightly longer than those of the cobalt atom to guanidonitrogen atoms [2.002(3)-2.020(3) Å]. The former is comparable to those found in dimeric 2-quinolyl-linked (thiophosphorano) methanide cobalt(II) [(CoCl{CH(iPr 2 PvS)(C 9 H 6 N-2)}) 2 ] (average Co-N quinolyl = 2.054 Å) 21 and the latter is comparable to those in bis(N,N′-diisopropylacetamidinate)cobalt(II) [Co( i Pr-MeAMD) 2 ] (average Co-N amidino = 2.012(8) Å). 22 The Co-Co distance of 4.146 Å is too long to consider having a bonding interaction (Co-Co distance with bonding interaction: 2.185-3.129 Å).…”

“…The tetrahedral Fe or Co centers in 3 or 4 are coordinated, respectively, by one chlorine atom, one nitrogen atom of the quinolyl ring in a κ-fashion and two nitrogen atoms of the bridging guanidinato moiety in a μ,η 1 :η 1 -fashion. For both 3 and 4, the MNCCN five-membered rings are essentially planar with a mean deviation of 0.0165 Å in 3 and In complex 3, the distances of the central iron atom to quinolyl nitrogen atoms [Fe1-N1 = 2.121(3) Å and Fe2-N5 = 2.122(3) Å] are slightly longer than those of the iron atom to guanidonitrogen atoms [2.018(2)-2.067(3) Å], and are also longer than those found in 2-quinolyl-linked(thiophosphorano)methanide iron(II) [Fe{CH(iPr 2 PvS)(C 9 H 6 N-2)} 2 ] (average Fe-N quinolyl = 2.052 Å) 21 and dimeric bis(N,N′-diisopropylacetamidinate)iron(II) ([Fe 2 (μ-i Pr-MeAMD) 2 -(η 2 -i Pr-MeAMD) 2 ]) (average Fe-N = 2.074(5) Å). 22 The Fe-Fe distance of 4.225 Å is too long to consider having a bonding interaction (Fe-Fe distance with bonding interaction: 2.64-3.04 Å).…”

“…24 From the X-ray structure of both 3 and 4, there is a 3.394 Å in 3 and 3.390 Å in 4, respectively, aromatic π-stacking interaction between two quinolyl rings, which further stabilizes the "openbox" framework structure. 21,25 The Li quinolyl guanidinate 2a reacted with an equimolar amount of (MeC 5 H 4 )TiCl 3 in Et 2 O to give dimeric titanium guanidinate 5 by a salt metathesis reaction and elimination of Me 3 SiCl (Scheme 3). After recrystallization from diethyl ether, complex 5 was obtained as crystals, in 73% yield.…”