Dimetalla-heterocyclic carbenes: The interconversion of chalcocarbonyl and carbido ligands

Article abstract of DOI:10.1039/d0cc05106c

The l-carbido complexes [Rh2(l-C)Cl2(PPh3)4] and [Rh2(l-C)Cl2(dppm)2] cleave CS2 to afford themonothiocarbonyl complexes [RhCl(CS)(PPh3)2] and [Rh2(l-CS)Cl2(dppm)2]. The latter reacts with dimethyl acetylenedicarboxylate (DMAD) to afford [Rh(l-CS)(l-DMAD)

Full text of DOI:10.1039/d0cc05106c

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DOI: 10.1039/D0CC05106C
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Dimetalla-Heterocyclic Carbenes: The Interconversion of
Chalcocarbonyl and Carbido Ligands
Harrison J. Barnett and Anthony F. Hill*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
The
C)Cl2(dppm)2] cleave CS2 to afford the monothiocarbonyl remains obscure. Attempts to extend this desulfurisation to
complexes [RhCl(CS)(PPh3)2] and [Rh2( -CS)Cl2(dppm)2]. The latter numerous other rhodium thiocarbonyl complexes or
reacts with dimethyl acetylenedicarboxylate (DMAD) to afford [IrCl(CS)(PPh3)2] have yet to find success. To generally explore
µ
-carbido complexes [Rh2(
µ
-C)Cl2(PPh3)4] and [Rh2(
µ
-
catecholborane1l however the mechanism of its formation,
µ
[Rh(
[Rh(
µ
µ
-CS)(
-C)(
µ
-DMAD)Cl2(dppm)2]. This complex is also formed from the reactivity of bridging carbido ligands and, more specifically,
µ
-DMAD)Cl2(dppm)2] and sulfur. These strategies also processes that involving carbon-chalcogen bond cleavage1d,k,o,2e
afford the first rhodium selenocarbonyl complexes [Rh(
CSe)Cl2(dppm)2] and [Rh( -CSe)( -DMAD)Cl2(dppm)2].
µ
-
or formation,4b we now discuss the reactions of dirhodium
carbido complexes with CS2 and chalcogens.
µ
µ
Documented reactions of metal-carbon multiple bonded
species with CS2 are somewhat scarce,5 being limited to the
inferred intermediacy of a thiocarbonyl-carbyne complex en
route to a thioketenyl;5a and the cleavage of CS2 by the carbyne
Binuclear µ-carbido complexes present four distinct bonding
scenarios (Chart 1) reflecting the effective atomic number
requirements (1-3 valence electrons) of the metal termini.1-4
complexes [Ru(
(R = C6H4Me-4; L = CO, PPh3; Tp = hydrotris(pyrazolyl)borate) to
afford the thiobenzoyl complex [Ru(
2-SCPh)Cl(CS)(PPh3)2]5b or
the thioketene complex [Mo( ’-SCCRCOS)(=O)(Tp)],
2-:h2
ºCPh)Cl(CO)(PPh3)2] and [Mo(ºCR)(CO)(L)(Tp)]
h
k
,s
respectively.5c For carbene complexes, Young has described a
thioketene pincer complex arising from the reaction of an
alkylidene pincer with CS2 and PPh3,5d while Bourissou has
observed the insertion of CS2 into a gold(III) carbene complex.5e
Treating complex 1 with CS2 at room temperature results
in spectroscopically quantitative formation to two equivalents
Chart 1. Distinct Bimetallic µ-Carbido Bonding Modes.1-4
Whilst an understanding of the bonding within bimetallic
carbidos is emerging1n,3g,4a,4b their reactivity remains essentially
uncharted. Reactivity studies are limited to various co-ligand
of the thiocarbonyl complex [RhCl(CS)(PPh3)2]6 (
2
, Scheme 1,
substitutions,1l,1m,2b,2g,3e,4a, oxidation to a CO ligand (Class
protonation to afford a
-methylidyne (Class B2b or D4b), CS2-
),2b halogenation to afford
-halocarbynes
A
),1l
1
CDCl3: dP = 31.0, JRhP = 142 Hz). There is no indication of the
formation of Ph3PS (dP » 35) confirming that the carbido ligand
serves as the sulfur abstracting agent for coordinated CS2. In
µ
insertion (Class
B
µ
1m
(Class
A)
and interconversion of bonding classes (Classes
D4a). For Class
-carbidos, the bent
contrast, treating
1 with elemental sulfur leads to complex
C
®
B3e,f and
A
®
D µ
degradation and formation of Ph3PS, without any observable
2
geometry at carbon renders it nucleophilic in reactions with
various electrophiles (CO2, MeOH, chalcogens, metals).4
being formed. Given that the reaction is accompanied by
complete rupture of the Rh=C=Rh spine, the reaction of the
dppm-bridged bimetallic complex [Rh2(µ-C)Cl2(µ-dppm)2] (3,
dppm = bis(diphenylphosphino)methane),1m with CS2 was
investigated. In general, two bridging dppm ligands confer
considerable stability on bimetallic ‘A-frame’ assemblies.7
Surprisingly, the product of this reaction was the
The Class
A complex [Rh2(µ-C)Cl2(PPh3)4] (1) is readily
accessible via the reaction of [RhCl(CS)(PPh3)2] (2) with
a Research School of Chemistry, Australian National University, Canberra,
Australian Capital Territory, ACT 2601, Australia. Email: a.hill@anu.edu.au
Electronic Supplementary Information (ESI) available: Synthetic procedures,
spectroscopic and crystallographic data. See DOI: 10.1039/x0xx00000x. CCDC
2013308 - 2013311 contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge Crystallographic
Data Centre.
coordinatively unsaturated mono-thiocarbonyl complex [Rh2(
CS)Cl2( -dppm)2] Figure S1), which could also be
spectroscopically observed to form when was treated with
µ-
µ
(4,
3
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contrast to CO it is extremely rare for thiocarbonyl ligands to
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simply dissociate,11 given the high energy of free CS.
DOI: 10.1039/D0CC05106C
The complex
form the
dppm)2] (
3
µ
also slowly reacts with elemental selenium to
2-selenocarbonyl complex [Rh2( -CSe)Cl2(
, Figure 1). Selenocarbonyl complexes remain rare11
a
µ
µ-
5
and group 9 examples are limited to an isoselenocarbonyl
complex12a and those derived from [IrCl(CSe)(PPh3)2].12b The
C=Se bond length of 1.747(8) Å is significantly shorter than the
imprecise bond lengths (R1 = 0.094) in the only other known
symmetrically bridging11e CSe complex [Ru2(
C5Me5)2] (1.802(13), 1.844(12) Å).4b Replacement of sulfur in
by selenium in
the Rh–Rh bond (mean 2.7754(9)Å cf, 2.7121(6) in
elongation is not computationally replicated for the model
complexes [Rh2( -CA)Cl2(dmpm)2] (A = O, S, Se; see ESI)
µ-CSe)(
µ-NPh)(h-
4
5
results in a significant (106 e.s.d.) elongation of
). This
4
µ
indicating the involvement of packing effects.
Scheme 1. Reactions of µ-carbido complexes with CS2 and chalcogens (R = CO2Me; i =
CS2, ii = HBO2C6H4, iii = 1/8 S8, iv = 1/n Sen, v = RCºCR.
elemental sulfur but not with methylthiirane (vide infra) nor
when [RhCl(CS)(PPh3)2] was treated with dppm. The
corresponding carbonyl analogue of
structural features of interest pertaining to the Rh2(
4
is well known8 and the
µ-CA) (A =
O,8c S) core are essentially comparable (Table S1). The Rh–Rh
bond length (2.7059(4)Å) is very marginally contracted upon
replacing oxygen by sulfur, while the Rh–C bond lengths are,
within precision limits, similar for both complexes. The bonding
within the Rh2CS unit is consistent with a canonical depiction
involving Rh–C and Rh–Rh single bonds on the basis of
experimentally determined mean bond lengths (1.915(6) and
2.7121(6) Å). These are not dissimilar to those calculated (DFT:
Figure 1. Molecular structure 5 in a crystal of 5.(PhMe)1.5 (50% displacement
ellipsoids, solvent and hydrogen atoms omitted, dppm groups simplified, one of
two crystallographically molecules shown, See Table S1, ESI). Selected bond lengths
(Å) and angles (°): Rh1–Rh2 2.7577(8), Rh1–Cl1 2.351(2), Rh1–C1 1.911(9), Rh2–C1
1.928(8), Se1–C1 1.747(8), C1–Rh1–Rh2 43.8(3), Rh2–C1–Rh1 91.8(4), Se1–C1–
Rh1 134.0(6). Insets: alternative views along and orthogonal to the Rh2C plane.
The reactions of terminal carbido complexes with
chalcogens have been shown to afford chalcocarbonyl
ligands2d,11e,13 and the formulation of a putative unstable Class
w
B97X-D/6-31G*/LANL2D
z
, 1.930 and 2.727 Å see ESI) for the
-CS)Cl2( -dmpm)2] (dmpm =
D
carbido has also been substantiated by its conversion to the
corresponding thio- are selenocarbonyl derivatives.4b The
isolable Class carbido [Rh2( -C)Cl2( -DMAD)( -dppm)2] (
hypothetical model complex [Rh2(
µ
µ
bis(dimethylphosphino)methane) which has Löwdin bond
orders of 1.12 (Rh–C) and 0.77 (Rh–Rh) and associated natural
charges of +0.48 (Rh), –0.55 (C) and –0.05 (S). The HOMO (See
D
µ
µ
µ
6,
DMAD = dimethyl acetylenedicarboxylate)4a displays a bent
(Rh–C–Rh = 124.7°) carbido ligand, the nucleophilicity of which
is manifest in reactions that append slender metal halides such
ESI Figure S10) comprises both Rh(dz ) orbitals and sulfur lone
2
pair character (alternative sites for electrophilic attack), while
the HOMO-1 and HOMO-4 orbitals contribute primarily to Rh–C
as AuCl and CuCl. The reaction of
room temperature primarily affords the thiocarbonyl complex
[Rh2( -CS)Cl2( -DMAD)( -dppm)2] ( ) in moderate yields that
6 with elemental sulfur at
and Rh–Rh
For the reactions of both
coordination of CS2 to one of the coordinatively unsaturated
rhodium centres (
, Scheme 1)9 followed by a cyclo-addition
with one Rh=C multiple bond via a hetero-alkene metathesis
mechanism (
, Scheme 1).5b,10 Ring cleavage of the metallacyclic
thione then generates two new thiocarbonyl ligands on
adjacent metals. For the reaction involving , a similar cleavage
s-bonding respectively.
µ
µ
µ
7
1
and 3 we envisage initial
were compromised by some degradation of the A-frame
architecture. Surprisingly, use of the typically milder single atom
sulfur transfer reagent methylthiirane14 led to complete
destruction of the complex such that dppm-S and dppm-S2 were
the predominant phosphorus-containing products observed
E
F
(31P NMR). An alternative synthesis of
facile addition of DMAD to (Scheme 1). All spectroscopic data
associated with indicate that it is C2v-symmetric in solution,
7 was achieved via the
3
3
would be expected to generate the unknown bimetallic species
[Rh2Cl2(CS)2(dppm)2] (cf. the known dicarbonyl analogue8), from
7
however attempts to grow crystals resulted in the isolation of
which dissociation of CS is required to provide 4. Notably, in
2 | Chem. Commun., 2018, 00, 1-3
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-1
the mono-aquo complex [Rh2(
dppm)2] (7a, Figure 2). Similar behaviour was encountered for
the trigonal carbido complexes [Rh2M( 3-C)Cl3(OH2)(
DMAD)( -dppm)2] (M = Cu, Au) such that while the water for
molecule does not remain bound in solution, the symmetry the infrared spectra of terminal selenocarbonyls, the
reduction (C2v Cs) upon coordination of water to a single is typically the most intense, however for and these modes
are weak, as could be computationally substantiated for the
model complexes [Rh2( -CSe)Cl2Ln] (Ln = dmpm, dHpm, (CO)4,
(CO)6) and [Rh2( -CSe)( -HCCH)Cl2(dmpm)2] (nCSe : 970-1030
cm-1; see ESI Table S1). The C1-Se1 bond length (1.785(6) Å) is
longer than in but still within the range found for terminal CSe
µ-CS)Cl2(OH2)(
µ-DMAD)(
µ-
assigned to a band of medium intensity at 1000 cm (cf. 957 cm-
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1
for 5
), that is absent in the precursor DaOndI: 1b0a.1s0e3d9/Do0nCRCe0d51li0c6hC-
µ
µ-
Teller considerations correlates with those found at 1249 cm-1
and 1700 cm-1 for [Rh2( -dppm)2].8b In
-CO)Cl2( -DMAD)(
CSe mode
µ
7
µ
µ
µ
n
®
5
8
rhodium impacts upon crystallisation.
µ
µ
µ
4
complexes (1.608-1.786Å)11,18 and shorter than found in NHC-
derived selenones (1.82-1.84 Å),17 or selenoureas, e.g., 1.844(4)
Å for(Me2N)2C=Se.19
Figure 2. Molecular structure 7a in a crystal of 7a.CHCl3 (50% displacement
ellipsoids, most hydrogen atoms omitted, dppm and ester groups simplified).
Selected bond lengths (Å) and angles (°): Rh1–Cl1 2.4741(12), Rh1–O1 2.300(4), Rh1–
C2 2.020(4), Rh1–C1 1.935(5), Rh2–C1 1.954(5), Rh2–C3 2.000(5), S1–C1 1.625(5),
C2–C3 1.350(7), Rh1–C1–Rh2 122.0(2), S1–C1–Rh1 130.3(3), S1–C1–Rh2 107.8(2).
Inset shows view orthogonal to the Rh2C plane.
Prior to the advent of
4 and 7a, structural data for
homobimetallic -thiocarbonyl ligands were somewhat
µ
Figure 3. Molecular structures of 8a in a crystal of 8a.(PhMe)(CH2Cl2)0.5, (50%
displacement ellipsoids, solvents and hydrogen atoms omitted, phenyl groups
simplified). Selected bond lengths (Å) and angles (°): Rh2–Se1 2.8947(8), Rh2–C1
1.935(6), Rh2–C3 2.008(6), Rh1–Cl1 2.4783(15), Rh1–O1 2.289(5), Rh1–C1
1.927(6), Rh1–C2 2.017(6), Se1–C1 1.785(6), Rh1–C1–Rh2 124.2(3), Se1–C1–Rh2
102.1(3), Se1–C1–Rh1 133.6(3). Inset Rh2CSe plane of 8a (blue) superimposed on that
of the precursor 6 (red).
sparse15 with none available for rhodium. Far more geometric
data for bridging chalcocarbonyls have however emerged from
extensive computational studies by King and Li.16 Symmetrical
µ-CS coordination is expected to weaken the CS multiple bond
and the CS bond lengths found for (1.619(4) Å) and 7a
4
(1.625(5)Å) fall towards the long end of the somewhat large
range (1.57515a to 1.629 Å4b). The Rh–C(S) bond lengths
primarily reflect the increase in rhodium coordination number
Turning to Ganter’s 77Se NMR derived parameters, we might
anticipate that the 77Se NMR spectrum of
8
comprises a single
15-line (tripled pentet, 103Rh and 31P: I = ½) resonance at ca dSe
= 530 ppm based on the HOMO-LUMO gap for . Unfortunately,
scanning the complete ~3000 ppm range for known selenium
proceeding from
coordinate (1.935(5) Å) rhodium centres in 7a
Class bent carbido complexes might be considered to in
4 (1.914(4) Å) to the five (1.954(5) Å) and six
6
.
D
shifts failed (as with dC) to identify a signal even employing a
133.4 MHz instrument, due to the high order coupling to 103Rh
and 31P (see ESI).
In conclusion, whilst CS2 has proven to be a valuable source
molecule for the installation of µ-carbido ligands in bimetallic
complexes,1d,1h,1n it is now found to be capable of undergoing
coupling reactions with established carbido ligands to
ultimately (re)generate thiocarbonyls. The addition of
some respects mimic isolobal N-heterocyclic carbenes (NHC),
not least in their ability to coordinate to extraneous metal
centres.4 To quantify the donor properties of the increasing
diversity of NHC ligands, Ganter has proposed employing the
77Se NMR shift of the corresponding selenone.17 The “carbene”
6
also reacts slowly with selenium (but not tellurium) to afford
inter alia [Rh2( -CSe)Cl2( -DMAD)( -dppm)2] ( , 14%). Whilst
the yield is disappointing, and are nevertheless the first
rhodium selenocarbonyl complexes and could also be formed
in an identical manner to through addition of DMAD to . As
with , the complex crystallises with a water molecule
coordinated to one rhodium centre, viz. [Rh2( -CSe)(OH2)Cl2(
DMAD)( -dppm)2] (8a, Figure 3). Recent developments in
selenocarbonyl and tellurocarbonyl chemistry have identified a
µ
µ
µ
8
5
8
chalcogens to a Class
construction of CS and CSe complexes further reinforcing the
Class /NHC analogy to provide the first rhodium
D µ-carbido complex has allowed the
8
7
5
D
7
selenocarbonyls.
µ
µ-
µ
Acknowledgements
diversity of bridging coordination modes,11e,18 though
5 and 8a
are two of only three complexes4b to display the symmetrical
bridging mode. The nCSe infrared absorption is tentatively
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Bourissou, N. Nebra, M. Fustier-Boutignon and N. Mezailles,
We gratefully acknowledge the Australian Research Council
(DP170102695 and DP190100723) for funding. The authors
declare no conflicts.
Angew. Chem., Int. Ed., 2017, 56, 12264-12267. View Article Online
DOI: 10.1039/D0CC05106C
6
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4 | Chem. Commun., 2018, 00, 1-3
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DOI: 10.1039/D0CC05106C
Table of Contents Text
Different classes of dirhodium -carbido
complexes cleave CS2 to afford mono- and bi-
nuclear CS complexes, the CSe analogues of which
are also described.
Table of Contents Graphic