Transition metal-mediated donor-acceptor coordination of low-oxidation state Group 14 element halides

Article abstract of DOI:10.1039/c5dt03018h

The reactivity of tungsten carbonyl adducts of Group 14 element (Ge, Sn and Pb) dihalides towards the metal-based donors (η⁵-C₅H₅)Rh(PMe₂Ph)₂ and Pt(PCy₃)₂ was examined. When (η⁵-C₅H₅)Rh(PMe₂Ph)₂ was treated with the Lewis acid supported Ge(ii) complex, THF·GeCl₂·W(CO)₅, cyclopentadienyl ring activation occurred, whereas the analogous Lewis acidic units SnCl₂·W(CO)₅ and PbCl₂ form direct adducts with the Rh complex to yield Rh-Sn and Rh-Pb dative bonds. Attempts to prepare metal coordinated element(ii) hydrides by adding hydride sources to the above mentioned rhodium-E(ii) halide complexes were unsuccessful; in each case insoluble products were formed along with regeneration of free (η⁵-C₅H₅)Rh(PMe₂Ph)₂. In a parallel study, ECl₂·W(CO)₅ (E = Ge or Sn) groups were shown to participate in E-Cl oxidation addition chemistry with (Cy₃P)₂Pt to give the formal Pt(ii) complexes ClPt(PCy₃)₂ECl·W(CO)₅.

Full text of DOI:10.1039/c5dt03018h

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Transition Metal-mediated Donor-acceptor Coordination of Low-
oxidation State Group 14 Element Halides
Received 00th January 20xx,
Accepted 00th January 20xx
Anindya K. Swarnakar, Michael J. Ferguson, Robert McDonald, and Eric Rivard*
DOI: 10.1039/x0xx00000x
www.rsc.org/
The reactivity of tungsten carbonyl adducts of Group 14 element (Ge, Sn and Pb) dihalides towards the metal-based
donors (η5-C5H5)Rh(PMe2Ph)2 and Pt(PCy3)2 was examined. When (η5-C5H5)Rh(PMe2Ph)2 was treated with the Lewis acid
supported Ge(II) complex, THF•GeCl2•W(CO)5, cyclopentadienyl ring activation occured, whereas the analogous Lewis
acidic units SnCl2•W(CO)5 and PbCl2 form direct adducts with the Rh complex to yield Rh-Sn and Rh-Pb dative bonds.
Attempts to prepare metal coordinated element (II) hydrides by adding hydride sources to the above mentioned rhodium-
E(II) halide complexes were unsuccesful; in each case insoluble products were formed along with regeneration of free (η5-
C5H5)Rh(PMe2Ph)2. In a parallel study, ECl2•W(CO)5 (E = Ge or Sn) groups were shown to participtate in E-Cl oxidation
addition chemistry with (Cy3P)2Pt to give the formal Pt(II) complexes ClPt(PCy3)2ECl•W(CO)5.
Russell’s synthesis of [(η5-C5H5)(CO)2Co HgCl2] in 1964,8
→
Introduction
various late metal MLBs based on Ir, Pt and Rh have been
developed.9 Moreover metal centered Lewis bases can readily
form stable coordinative interactions with electron deficient
Group 13 (B, Al and Ga)10 and Group 14 (Ge, Sn and Pb)11
compounds. Herein we explore the ability of the half sandwich
complex CpRh(PMe2Ph)2 (Cp = η5-C5H5)12 and the nucleophilic
Pt(0) donor Pt(PCy3)2 to interact with divalent Group 14
species. An ultimate goal of this program would be to generate
mixed metal donor-acceptor complexes of EH2 units (E = Ge, Sn
and Pb) for the later preparation of binary ExMy (M = metal)
bulk or nanomaterials.13
A central concept in synthetic inorganic chemistry is the use of
electron-donating ligands to bind/stabilize reactive inorganic
species with unusual bonding environments. In this regard N-
heterocyclic carbenes (NHCs) such as IPr ([(HCNDipp)2C:]; Dipp
= 2,6-iPr2C6H3) and their structural analogues have been used
to intercept novel main group species such as B2 and the
homologous ditetrelene series :E=E: (E = Si, Ge and Sn).1,2 Also
of relevance to this paper is our use of NHCs in conjunction
with various Lewis acidic capping units to coordinate the
inorganic methylene analogues :EH2 (E = Si, Ge, and Sn) via a
general donor-acceptor approach (e.g. IPr•GeH2•BH3).3 In
addition, we have extended this protocol to include EH2
complexes supported by the N-heterocyclic olefin (NHO)
IPr=CH2 and the Wittig reagent Ph3P=CMe2.4 Interest in these
complexes stems from the formation of EH2 as intermediates
en route to bulk semi-conductors and metals via tetrelane
(EH4) degradation.5 Moreover we have recently demonstrated
that luminescent Ge nanoparticles could be prepared from the
mild, one pot, decomposition of the donor-acceptor GeH2
complex Ph3PCMe2•GeH2•BH3.6
Results and discussion
We began our study with an attempt to synthesize a GeCl2
donor-acceptor complex using CpRh(PMe2Ph)2 as a Lewis base
and W(CO)5 as
a capping Lewis acid. However when
THF•GeCl2•W(CO)5 was combined with CpRh(PMe2Ph)2 in
toluene for 12 hrs, the resulting deep yellow solid gave
spectroscopic signatures consistent with C-H bond activation
of the cyclopentadienyl ligand. Specifically, a highly upfield
positioned doublet of triplet resonance was found at -11.98
Metal centered Lewis bases (MLBs), wherein an
electron rich metal center acts as a formal two-electron donor,
are being increasingly investigated within the context of
supporting low-oxidation state main group element
chemistry.7 A possible advantage of MLBs over traditional
organic-based donors is the ability to dramatically alter the
coordination properties of a MLB via co-ligand modification
and/or by changing the metal entirely. Since Nowell and
1
1
ppm in the H NMR spectrum in CD2Cl2 (2JH-P = 29.9 Hz and JH-
= 19.9 Hz), indicating that hydrogen migration to yield a
Rh
terminal Rh-H group transpired. Moreover two distinct Cp-H
resonances of equal intensity were noted at 5.40 and 5.75
ppm, respectively, consistent with a mono-functionalized Cp
unit. X-ray crystallography later confirmed that hydrogen
migration/Cp ring activation did occur to form the Rh(III)
product [(CO)5W•GeCl2(η5-C5H4)]RhH(PMe2Ph)2
(1) (eqn. (1),
Fig. 1). A related hydride migration/Cp activation process was
noted when CpRh(PMe3)2 was treated with the bulky alkyl
a.Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive,
Edmonton, Alberta, Canada T6G 2G2.
t
i
halides BuI or PrI, affording the alkylated-cyclopentadienyl
t
i
rhodium salts [(η5-C5H4R)RhH(PMe3)2]I (R = Bu or Pr).14 It is
likely that the high electrophilicity of the GeCl2•W(CO)5 unit
promotes attack at the Cp ring in CpRh(PMe2Ph)2, followed by
†Electronic supplementary information (ESI) available: Tables of crystallographic
data for compounds 1-6. CCDC 1416191-1416196. For ESI and crystallographic data
in CIF or other electronic format see DOI: XXXX.
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proton transfer to the basic Rh center. As shown in Fig. 1,
Following a related protocol as what was just discussed,
[(CO)5W•GeCl2(η5-C5H4)]RhH(PMe2Ph)2 (
1
) has a GeCl2•W(CO)5 the clean formation of the metal only Lewis pair
group directly attached to a Cp ring with a Ge-C bond distance CpRh(PMe2Ph)2•PbCl2 ( ) was accomplished by combining an
of 1.9709(19) Å; this value is similar to the covalent Ge-C bond equimolar amount of PbCl2 with CpRh(PMe2Ph)2 in toluene
length found within Power’s aryl(halo)digermene (eqn. (3)). Two broad methyl resonances from the PMe2Ph
3
ArMesGe(Cl)Ge(Cl)ArMes [2.000(6) Å] (ArMes = 2,6-Mes2C6H3; Mes ligands were located at 1.42 and 1.62 ppm in the 1H NMR
= 2,4,6-Me3C6H2).15 The Ge-W interaction in
and is the same within experimental error as the average Ge- spectrum afforded a doublet signal at 8.2 ppm with a JRh-P
1
is 2.5820(2) Å spectrum of
3
in CD2Cl2, while the corresponding 31P{1H} NMR
1
W distance of 2.5833(16) Å in IPr•GeCl2•W(CO)5.16 The hydride constant of 170 Hz.
bound to the Rh center in 1 could be located in the electron
difference map and the refined Rh-H bond length [1.51(3) Å] is
of similar value as in Cp2Zr(CH2PPh2)2Rh(H)(PPh3) [1.51(4) Å].17
Fig. 2. Molecular structure of CpRh(PMe2Ph)2•SnCl2•W(CO)5 (2)
with thermal ellipsoids presented at a 30 % probability level; all
hydrogen atoms have been omitted for clarity. Selected bond
lengths (Å) and angles (deg): Rh-Sn 2.6152(5), Sn-Cl(1) 2.4544(14),
Sn-Cl(2) 2.4685(15), Sn-W 2.7736(4); Rh-Sn-W 134.438(17), Cl(1)-
Sn-Cl(2) 91.60(6).
The crystallographically determined structure of compound
is shown in Fig. 3. and displays a highly pyramidalized lead
3
center [ ° at Pb (avg.) = 296.7°] with a Rh-Pb bond length of
Fig.
1.
Molecular
structure
of
[(CO)5W•GeCl2(η5-
Σ
2.7561(7) Å; this is, to our knowledge, the first structural
characterization of such a bond.
C5H4)]RhH(PMe2Ph)2 (1) with thermal ellipsoids presented at a 30 %
probability level. All carbon-bound hydrogen atoms have been
omitted for clarity. Selected bond lengths (Å) and angles (deg): Rh-
H(1) 1.51(3), Ge-C(6) 1.9709(19), Ge-Cl(1) 2.2464(5), Ge-Cl(2)
2.2324(5), Ge-W 2.5820(2); Cl(1)-Ge-Cl(2) 96.62(2), C(6)-Ge-W
129.52(6), Ge-C(6)-Rh 123.82(9), Ge-C(6)-Rh 123.82(9).
A
different reactivity profile was noted when
CpRh(PMe2Ph)2 was combined with the Sn(II) dihalide adduct
(THF)2SnCl2•W(CO)5. In this case the resulting yellow-orange
solid did not yield any spectroscopic evidence for Rh-H bond
formation. The 1H NMR spectrum of the product in CDCl3
contained two virtual triplet resonances assigned to two
diastereotropic methyl groups within the phosphine ligands (at
1.92 and 2.08 ppm), while one Cp environment was present, as
evidenced by a singlet resonance at 5.25 ppm. Crystals of
suitable quality for X-ray analysis were subsequently obtained
and conclusively identified the product as the expected Lewis
Figure 3. Molecular structure of CpRh(PMe2Ph)2•PbCl2 (3) with
thermal ellipsoids presented at
a 30 % probability level; all
hydrogen atoms have been omitted for clarity. Selected bond
lengths (Å) and angles (deg) with parameters associated with a
second molecule in the asymmetric unit listed in square brackets:
Rh(1A)-Pb(1A) 2.7561(7) [2.7530(7)], Pb(1A)-Cl(1A) 2.6314(16)
[2.6540(16)], Pb(1A)-Cl(2A) 2.6515(16) [2.6489(16)]; Cl(1A)-Pb(1A)-
Cl(2A) 95.65(6) [98.91(6)], Rh(1A)-Pb(1A)-Cl(1A) 99.78(4) [111.8(2)],
Rh(1A)-Pb(1A)-Cl(2A) 101.25(4) [97.48(4)].
acid-base adduct CpRh(PMe2Ph)2•SnCl2•W(CO)5 (2) (eqn. (2)).
The molecular structure of (Fig. 2) shows a Rh-Sn single bond
2
distance of 2.6152(5) Å, which is comparable to the terminal
Rh-Sn linkage reported within mer-[{Rh(CNC8H9)3(SnCl3)(μ-
SnCl2)}2] [2.606(1) Å].18 The Rh-Sn bond in
2 is however
elongated compared to the Rh-Sn bonds within Marder’s Sn(II)
bis-adduct Cl2Sn[Rh(PMe3)3Cl]2 [2.712(1) Å].11a
2 | J. Name., 2012, 00, 1-3
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Positing that the soft-soft coordinative Rh-Pb interactions
might still support the formation of a Pb(II) hydride
complex at a later stage, CpRh(PMe2Ph)2•PbCl2 ( ) was treated
in
3
3
with different Lewis acids in an attempt to form the Pb(II)
dihalide precursors CpRh(PMe2Ph)2•PbCl2•LA (LA = Lewis acid).
We initially reacted compound 3 with an equimolar amount of
THF•GeCl2•W(CO)5 with the goal of producing the formal
CpRh(PMe2Ph)2•Cl-
was treated with one
We decided to react compounds 1-3 with various hydride
tetrahalodimetallene
2PbGeCl2•W(CO)5. However, when
complex
sources to gain access to new metal-supported EH2 complexes
(E = Ge, Sn or Pb). Motivated by our prior successes with using
Li[BH4] to generate donor-acceptor complexes of Group 14
dihydrides (e.g. IPr•SnH2•W(CO)5),3a,4a we first treated
3
equivalent of THF•GeCl2•W(CO)5, the clean formation of the
previously synthesized Cp-ring activation product
[(CO)5W•GeCl2(η5-C5H4)]RhH(PMe2Ph)2
transpired along
(1)
CpRh(PMe2Ph)2•SnCl2•W(CO)5 (2) with two equivalents of
with the expulsion of PbCl2 from the coordination sphere of
rhodium (Scheme 2). In another effort to obtain a donor-
acceptor complex of PbCl2, the bulky fluorinated arylborane
Li[BH4] in Et2O. The resulting reaction proceeds with the
immediate formation of an insoluble black precipitate,
presumably consisting of metallic tin and/or tin-tungsten
clusters; the only product found in the colorless supernatant
was the known phosphine-borane adduct, PhMe2P•BH3.19 The
formation of PhMe2P•BH3 likely occurs via PhMe2P
decomplexation from rhodium and coordination to the Lewis
acidic by-product BH3 that is generated from Li[BH4] during Cl-
/H- exchange. As a result, we chose not to explore Li[BH4] as a
(BArF ) (ArF = 3,5-(F3C)2C6H3) was combined with compound
3.
3
Interestingly, this reaction afforded a new product with a Rh-H
1H NMR resonance at -11.58 ppm in C6D6 (doublet of triplet
pattern), consistent with
occurring as in the formation of
a
related C-H bond activation
. Furthermore, the presence
1
1
of two distinct Cp resonances in the H NMR spectrum and an
accompanying 11B NMR signal in the region expected for four-
coordinate boron (-10.1 ppm), suggested that electrophilic
hydride source for the related adducts 1 and 3. In order to
obviate phosphine dissociation from Rh, the alkylated borate
salt K[HBsBu3] was selected as a hydride delivery agent as after
attack at Cp by BArF happened. Fortunately colorless crystals
3
of the product could be obtained and X-ray crystallography
confirmed the formation of the Cp ring-activated Rh(III)
s
H-/Cl- exchange, the resulting by-product, Bu3B, is a hindered
borane of low Lewis acidity.20 However when compounds
1-3
complex [η5-C5H4BArF ]RhH(PMe2Ph)2 (
4
) (Scheme 2, Fig. 4). An
was also accomplished by
combining an equimolar mixture of CpRh(PMe2Ph)2 and BArF
3
were separately treated with two equivalents of K[HBsBu3], the
regeneration of free CpRh(PMe2Ph)2 occurred in all cases
independent synthesis of
4
3
(Scheme
C5H4)]RhH(PMe2Ph)2
1).
Of
note,
when
[(CO)5W•GeCl2(η5-
in toluene. The noted inability of the Pb center in
W(CO)5 is likely due to the lower nucleophilicity of Pb(II)
3 to bind to
(
1
) was treated with K[HBsBu3], the
centers in relation to Sn(II) (i.e. the inert pair effect).3e
formal hydrogen transfer from Rh back to the Cp ring was
noted, along with the cleavage of C(Cp)-Ge bond, leading to
CpRh(PMe2Ph)2 formation.
The molecular structure (Fig. 4) of compound
H bond distance of 1.50(3) Å, which is of similar value as the
Rh-H bond length in compound . The C(Cp)-B bond distance in
4 shows a Rh-
1
4
was found to be 1.636(3) Å which is elongated in comparison
to the C(Cp)-B interaction of 1.545(3) Å in [(C6F5)2B(η5-
C5H4)]TiCl3.21
We also briefly explored the chemistry of another metal
22
centered Lewis base Pt(PCy3)2 towards Group 14 dihalide
complexes.
First,
Pt(PCy3)2
was
treated
with
THF•GeCl2•W(CO)5 in toluene. In place of 1:1 adduct
formation, oxidative addition of the Ge-Cl bond at Pt occurs
affording ClPt(PCy3)2Ge(Cl)•W(CO)5 (5) as a yellow, moisture-
sensitive solid. Recently Braunschweig, Jones and coworkers
reported the formation of the Lewis acid-base adduct,
(Cy3P)2Pt•GeCl2 from the direct interaction of Pt(PCy3)2 with
Cl2Ge•dioxane.11d However the presence of a Lewis acidic
W(CO)5 unit at the Ge(II) center facilitates Ge-Cl bond oxidative
addition to form 5 (eqn. (4)). Similar oxidative additions
involving electron deficient BX3 (X = Cl, Br or I),23 GaX3 (X = Br
25
or I),24 and BiCl3 to Pt(0) complexes are known. The crystal
structure of 5 is presented in Fig. 5 and shows a Pt-Ge bond
distance of 2.3526(5) Å, which is somewhat contracted in
length in comparison to the Pt-Ge distance in (PCy3)2Pt•GeCl2
[2.397(1) Å].11d The overall geometry at Pt is square planar,
consistent with a Pt(II) formal oxidation state, while the
proximal Ge center adopts a distorted T-shaped geometry with
a stereochemically active lone pair (e.g. Pt-Ge-Cl(2) angle =
Scheme 1. Reactivity of compounds 1-3 with K[HBsBu3]. The fate of
the W(CO)5 units and tetrel elements (Ge and Sn) in these reactions
is unknown.
104.87(2)°). The 31P{1H} NMR spectrum of
5 in C6D6 yields a
resonance at 16.9 ppm with resolvable platinum satellites (1JP-
Pt = 2412 Hz).
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hydride source, K[HBsBu3] with the intention of yielding a ClPt(PCy3)2Sn(Cl)•W(CO)5
stable Ge(II) hydride complex. However upon hydride addition, mixture and identified by X-crystallography (Fig. 6). Compound
the only species identified in the 31P{1H} NMR spectrum of the
likely forms via the oxidative addition of a Sn-Cl bond to a
. The
shows a square planar Pt environment
5
was also combined with two equivalents of products from each other, a crystal of one of the products,
(
6), was selected from the product
6
resulting product mixture was free PCy3; the formation of Pt(0) center, in similar fashion as for the Ge congener
5
sBu3B was also confirmed by 11B NMR spectroscopy.
molecular structure of 6
with a Pt-Sn bond distance of 2.5061(3) Å, which is shorter
than the reported dative Pt-Sn bond in (Cy3P)2Pt•SnCl2
[2.599(1) Å].11d It is likely that the other species present in the
abovementioned reaction mixture is the non-activated adduct
(Cy3P)2Pt•SnCl2•W(CO)5. To see if one species could be
converted into the other, the product mixture was heated in
C6D6 at 50 °C for 5 hours, however no change in the relative
ratio of intensities of two signals in the resulting 31P{1H} NMR
spectrum was found. At higher temperatures (> 80 °C) both
species decompose to yield multiple new species (ca. 10) from
which no clean product could be isolated.
Scheme 2. Reactivity of 3 with different Lewis acids, leading to C-H
bond activation.
Figure 5. Molecular structure of ClPt(PCy3)2Ge(Cl)•W(CO)5 (5) with
thermal ellipsoids presented at
a 30 % probability level; all
hydrogen atoms have been omitted for clarity. Selected bond
lengths (Å) and angles (deg): Pt-Ge 2.3526(5), Ge-Cl(2) 2.2489(9),
Pt-Cl(1) 2.4176(8), Ge-W 2.5745(5); Cl(1)-Pt-Ge 176.20(2), Pt-Ge-
Cl(2) 104.87(2), Pt-Ge-W 147.463(10).
Fig. 4. Molecular structure of [η5-C5H4BArF ]RhH(PMe2Ph)2 (4) with
3
thermal ellipsoids presented at a 30 % probability level; all carbon-
bound hydrogen atoms have been omitted for clarity. Selected
bond lengths (Å) and angles (deg): B-C(1) 1.636(3), Rh-H 1.50(3); B-
C(1)-Rh 132.18(13), average C(1)-B-C(ArF) = 109.5 (3).
The bis(phosphine) complex Pt(PCy3)2 was then mixed with
one equivalent of (THF)2SnCl2•W(CO)5, resulting in the
formation of two different Pt(PCy3)2-containing products by
31P{1H} and 195Pt{1H} NMR spectroscopy. Specifically, the
31P{1H} NMR spectrum of the product mixture afforded two
resonances in a 7:3 ratio with resolvable 195Pt satellites at 26.1
(1JP-Pt = 2392 Hz) and 47.4 (1JP-Pt = 3063 Hz) ppm. Whereas the
195Pt{1H} NMR spectrum gave two different triplets at -3725
Fig. 6 Molecular structure of ClPt(PCy3)2Sn(Cl)•W(CO)5 (6) with
thermal ellipsoids presented at
a 30 % probability level; all
hydrogen atoms have been omitted for clarity. Selected bond
lengths (Å) and angles (deg): Pt-Sn 2.5061(3), Sn-Cl(2) 2.4149(11),
Pt-Cl(1) 2.4110(11), Sn-W 2.7309(3); Cl(1)-Pt-Sn 172.63(3), Pt-Sn-
Cl(2) 107.89(3), Pt-Sn-W 144.019(13).
= = 3056 Hz) ppm.
(1JP-Pt 2395 Hz) and -4543 (1JP-Pt
Unfortunately we were not able effectively separate these two
4 | J. Name., 2012, 00, 1-3
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or Patterson search/ structure expansion facilities within the
DIRDIF-2008 program
suite32 ([(CO)5W•GeCl2(η5-
C5H4)]RhH(PMe2Ph)2 ), (CpRh(PMe2Ph)2•SnCl2•W(CO)5 )),
structure refinement was accomplished using either SHELXL-97
or SHELXL-2013.31 All carbon-bound hydrogen atoms were
assigned positions on the basis of the sp2 or sp3 hybridization
geometries of their attached carbon atoms, and were given
thermal parameters 20 % greater than those of their parent
Conclusions
In conclusion, the reactivity of the metal centered Lewis basic
complexes CpRh(PMe2Ph)2 and Pt(PCy3)2 towards various
electron deficient E(II) dihalide units (E = Ge, Sn and Pb) was
explored. When strong Lewis acids were combined with the Rh
complex CpRh(PMe2Ph)2 the formation of Cp-activated
products and Rh-H bonds occurred in place of direct Rh-E bond
formation. In the case of Pt(PCy3)2, the formal oxidation
addition of Ge-Cl and Sn-Cl bonds transpired to give the
products ClPt(PCy3)2E(Cl)•W(CO)5 (E = Ge and Sn). Attempts to
form the corresponding Group 14 hydrides via H- addition to E-
Cl residues were unsuccessful, and in each case hydride
(
1
(2
atoms. For compounds 1, and 4, all hydrogen atoms attached
to heteroatoms (Rh) were located from difference Fourier
maps, and their coordinates and isotropic displacement
parameters were allowed to refine freely.
addition to the Rh complexes
1
-
3
afforded free
Synthetic details.
Synthesis of [(CO)5W•GeCl2(η5C5H4)]RhH(PMe2Ph)2 (
1
). A 3 mL
toluene solution of CpRh(PMe2Ph)2 (33 mg, 0.074 mmol) was
added dropwise to mL toluene solution of
CpRh(PMe2Ph)2. Future work will involve tailoring the nature
of the metal centered Lewis bases and Lewis acidic partner to
obtain viable EH2 precursor complexes for mixed element
deposition processes.
a
3
(THF)•GeCl2•W(CO)5 (40 mg, 0.074 mmol), and the mixture
was stirred overnight. The resulting dark yellow precipitate
was separated from the mother liquor, washed with 5 mL of
hexanes and dried under vacuum. Pure product was obtained
by crystallization from hexanes/CH2Cl2 at -35 °C. Yield: 30 mg
Experimental Details
Materials and Instrumentation.
(45 %). 1H NMR (500 MHz, CD2Cl2):
δ = 7.42-7.48 (m, 2H, ArH),
7.34-7.42 (br, 4H, ArH), 7.18-7.27 (m, 4H, ArH), 5.75 (s, 2H, Cp),
All reactions were performed using standard Schlenk line
techniques under an atmosphere of nitrogen or in an inert
atmosphere glovebox (Innovative Technology, Inc.). Solvents
were dried using a Grubbs-type solvent purification system26
manufactured by Innovative Technology, Inc., degassed
(freeze−pump−thaw method), and stored under an
atmosphere of nitrogen prior to use. Li[BH4], K[HBsBu3] (1.0 M
solution in THF), and PbCl2 were purchased from Aldrich and
used as received. (THF)2SnCl2•W(CO)5,27 THF•GeCl2•W(CO)5,16
CpRh(PMe2Ph)2,12 BArF3 (ArF = 3,5-(F3C)2C6H3),28 and (Cy3P)2Pt22
were prepared according to literature procedures. 1H, 11B,
13C{1H}, 31P{1H}, 19F{1H}, 119Sn and 195Pt NMR spectra were
recorded on a Varian iNova- 400 spectrometer and referenced
externally to SiMe4 (1H and 13C{1H}), 85 % H3PO4 (31P{1H}),
5.40 (s, 2H, Cp), 1.65 (vt, N = ǀ2JH-P + JH-Pǀ = 8.4 Hz, 6H, CH3),
4
1.54 (vt, N = ǀ2JH-P + JH-Pǀ = 8.4 Hz, 6H, CH3), -11.98 (dt, JH-P
=
4
2
1
29.9 Hz, JH-Rh = 19.9 Hz, 1H, Rh-H). 13C{1H} NMR (125 MHz,
CD2Cl2):
δ
= 202.6 (s, COax), 199.1 (s, COeq, satellite: 1JC-W = 124
Hz), 135.0 (vt, N = ǀ1JC-P + JC-Pǀ = 53.6 Hz, ArC), 130.8 (s, ArC),
130.2 (s, ArC), 128.8 (s, ArC), 94.4 (s, Cp), 90.1 (s, Cp), 22.1 (vt,
N = 34.1 Hz, CH3), 21.0 (vt, N = 37.9 Hz, CH3). 31P{1H} NMR (161
3
1
1
MHz, CD2Cl2): δ = 14.6 (d, JP-Rh = 139 Hz). H NMR (500 MHz,
CDCl3): = 7.41-7.49 (m, 2H, ArH), 7.33-7.41 (m, 4H, ArH),
δ
7.14-7.28 (m, 4H, ArH), 5.66 (s, 2H, Cp), 5.43 (s, 2H, Cp), 1.65
(vt, N = ǀ2JH-P + 4JH-Pǀ = 10 Hz, 6H, CH3), 1.56 (vt, N = ǀ2JH-P + 4JH-P
ǀ
= 10 Hz, 6H, CH3), -11.92 (dt, Rh-H, 2JH-P = 29.9 Hz, JH-Rh = 19.9
1
F3B•OEt2 (11B), CFCl3 (19F{1H}), SnMe4 (119Sn), and Na2[PtCl6] in Hz, 1H, Rh-H). 31P{1H} NMR (161 MHz, CDCl3):
δ
= 14.1 (d, 1JP-Rh
D2O (195Pt) respectively. Elemental analyses were performed = 139.1 Hz). IR (Nujol, cm−1): 1901 (br, υCO), 1970 (s, υCO), 2059
by the Analytical and Instrumentation Laboratory at the (s, υCO). Anal. Calcd. for C26H27Cl2GeO5P2RhW: C, 34.25; H, 2.98.
University of Alberta. Infrared spectra were recorded on a Found: C, 34.25; H, 3.14. Mp (°C): 132-135 (decomposes).
Nicolet IR100 FTIR spectrometer as Nujol mulls between NaCl
plates. Melting points were measured in sealed glass Synthesis of CpRh(PMe2Ph)2•SnCl2•W(CO)5 (
capillaries under nitrogen using a MelTemp melting point solution of CpRh(PMe2Ph)2 (18 mg, 0.041 mmol) was added
2). A 3 mL toluene
apparatus and are uncorrected.
dropwise to a 3 mL toluene solution of (THF)2SnCl2•W(CO)5 (36
mg, 0.045 mmol), and the mixture was stirred overnight. The
resulting orange yellow precipitate was separated from the
mother liquor, washed with 5 mL of hexanes and dried under
vacuum. Yield: 38 mg (94 %). Crystals suitable for X-ray
X-ray Crystallography. Crystals of suitable quality for X-ray
diffraction studies were removed from a vial in a glovebox and
immediately covered with a thin layer of hydrocarbon oil
(Paratone-N). A suitable crystal was selected, mounted on a
glass fiber, and quickly placed in a low temperature stream of
nitrogen on an X-ray diffractometer.29 All data were collected
at the University of Alberta using a Bruker APEX II CCD
detector/D8 diffractometer using Mo Kα, [(CO)5W•GeCl2(η5-
1
crystallography were grown from CH2Cl2/hexanes at -35 °C. H
NMR (500 MHz, CDCl3):
(m, 4H, ArH), 7.14-7.22 (m, 4H, ArH), 5.25 (s, 5H, Cp), 2.08 (vt,
δ = 7.44-7.50 (m, 2H, ArH), 7.36-7.44
N = 10 Hz, 6H, CH3), 1.92 (vt, N = 10 Hz, 6H, CH3). 13C{1H} NMR
(125 MHz, CDCl3): δ = 203.0 (s, COax), 200.7 (s, COeq), 139.6 (vt,
N = 48.6 Hz, ArC), 130.7 (s, ArC), 129.5 (s, ArC), 129.1 (s, ArC),
C5H4)]RhH(PMe2Ph)2
ClPt(PCy3)2GeCl•W(CO)5 (
(CpRh(PMe2Ph)2•SnCl2•W(CO)5
C5H4BArF ]RhH(PMe2Ph)2 (
(
5
1
),
), ClPt(PCy3)2SnCl•W(CO)5 (
),
CpRh(PMe2Ph)2•PbCl2
(3),
)) or Cu
6
95.1 (s, Cp), 22.9 (vt, N = 35.9 Hz, CH3), 15.6 (vt, N = 35.8 Hz,
1
Kα
(
2
[η5-
CH3). 31P{1H} NMR (201 MHz, CDCl3):
δ
= 4.6 (d, JRh-P = 153 Hz,
3
3
satellites: JP-W = 77 Hz). IR (Nujol, cm−1): 1892 (br, υCO), 1965
(s, υCO), 2054 (s, υCO). Anal. Calcd. for C26H27Cl2O5P2RhSnW: C,
32.60; H, 2.84. Found: C, 32.42; H, 2.92. Mp (°C): 150-153
(decomposes).
4)) radiation with the crystals cooled
to −100 °C. The data were corrected for absorption through
Gaussian integration from the indexing of the crystal faces.30
Structures were solved using intrinsic phasing SHELXT31
(CpRh(PMe2Ph)2•PbCl2
ClPt(PCy3)2GeCl•W(CO)5
(
(
3
5
), [η5-C5H4BArF ]RhH(PMe2Ph)2
), and ClPt(PCy3)2SnCl•W(CO)5
(
4
),
3
(
6)),
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DOI: 10.1039/C5DT03018H
ARTICLE
Journal Name
Synthesis of CpRh(PMe2Ph)2•PbCl2 (3). A 3 mL toluene solution solvent was removed from the filtrate to yield an orange oil
of CpRh(PMe2Ph)2 (68 mg, 0.15 mmol) was added dropwise to containing a mixture of CpRh(PMe2Ph)2 and sBu3B.
a 3 mL toluene suspension of PbCl2 (51 mg, 0.18 mmol), and
the mixture was stirred overnight. The solvent was removed Reaction of CpRh(PMe2Ph)2•PbCl2 (
3
) with K[HBsBu3]. To a 5 mL
(56 mg, 0.077 mmol) was added
under vacuum and the remaining red powder was washed toluene solution of
3
twice with 5 mL portions of hexanes and dried. The red solid K[HBsBu3] (178 μL, 1.0 M solution in THF, 0.18 mmol), and the
was then dissolved in 10 mL of CH2Cl2 and the resulting mixture was stirred overnight. The mother liquor was
solution was filtered. The solvent was removed from the separated from the grey precipitate by filtration and the
filtrate and the product was dried under vacuum. Yield: 65 mg solvent was removed from the filtrate to yield an orange oil
(60 %). Crystals suitable for X-ray crystallography were grown consisting of a mixture of CpRh(PMe2Ph)2 and sBu3B.
1
from hexanes/THF at -35 °C. H NMR (500 MHz, CD2Cl2):
δ =
7.41-7.58 (m, 6H, ArH), 7.22-7.38 (m, 4H, ArH), 5.11 (s, 5H, Cp),
Reaction of CpRh(PMe2Ph)2•PbCl2 (3) with THF•GeCl2•W(CO)5.
1.62 (br, 6H, CH3), 1.42 (br, 6H, CH3). 13C{1H} NMR (125 MHz,
A 3 mL toluene solution of THF•GeCl2•W(CO)5 (25 mg, 0.043
mmol) was added dropwise to a 3 mL toluene suspension of
CpRh(PMe2Ph)2•PbCl2 (31 mg, 0.043 mmol) and the mixture
was stirred overnight. The solvent was removed under vacuum
from the black suspension to give a black powder. The only
soluble product identified by 1H and 31P{1H} NMR was [η5-
CD2Cl2): δ = 136.7 (vt, N = 46.9 Hz, ArC), 130.6 (s, ArC), 129.9 (s,
ArC), 129.3 (s, ArC), 94.0 (s, Cp), 22.1 (vt, N = 33.7 Hz, CH3),
15.4 (vt, N = 33.4 Hz, CH3). 31P{1H} NMR (201 MHz, CD2Cl2):
δ =
1
8.2 (d, JRh-P = 170 Hz). Anal. Calcd. for C21H27Cl2P2PbRh: C,
34.92; H, 3.77. Found: C, 35.07; H, 3.76. Mp (°C): 185-188
(decomposes).
C5H4GeCl2•W(CO)5]RhH(PMe2Ph)2 (1).
Reaction of CpRh(PMe2Ph)2•PbCl2
toluene solution of BArF (40 mg, 0.062 mmol) was added
(3
) with BArF . A 3 mL
3
Synthesis of [η5-C5H4BArF ]RhH(PMe2Ph)2
solution of CpRh(PMe2Ph)2 (83 mg, 0.19 mmol) was added
(
4
). A 3 mL toluene
3
3
dropwise to a 3 mL toluene solution of BArF (136 mg, 0.19
dropwise to
a
3
mL toluene suspension of
3
CpRh(PMe2Ph)2•PbCl2 (45 mg, 0.062 mmol) and the mixture
was stirred overnight. The solvent was removed under vacuum
from the black suspension to obtain a black powder. The only
mmol) and the mixture was stirred overnight to give a red
solution. The solvent was removed from the mixture under
vacuum to afford a deep yellow-orange oil. The oil was re-
dissolved in 3 mL of Et2O and the solvent was removed anew
to yield an orange powder. This product was then washed with
NMR identified product was [η5-C5H4BArF ]RhH(PMe2Ph)2 (
4).
3
Synthesis of ClPt(PCy3)2GeCl•W(CO)5 (
5). A solution of Pt(PCy3)2
a mixture of Et2O/hexanes (1 mL + 3 mL) to give 4 as a white
powder. Yield: 100 mg (48 %). Crystals suitable for X-ray were
grown from hexanes/Et2O at -35 °C C. 1H NMR (500 MHz,
C6D6): δ = 8.27 (s, 6H, o-C6H3(CF3)2), 7.80 (s, 3H, p-C6H3(CF3)2),
6.89-6.92 (m, 6H, ArH), 6.55-6.75 (m, 4H, ArH), 4.70 (s, 2H, Cp),
(180 mg, 0.24 mmol) in 3 mL of toluene was added dropwise
to a 3 mL toluene solution of THF•GeCl2•W(CO)5 (130 mg, 0.24
mmol). The reaction mixture was stirred for 24 hrs and the
solvent was removed under vacuum. Then 5 mL of hexanes
was added to the oily product followed by stirring for one
hour. The precipitate was separated from the mother liquor
and dried under vacuum to give a yellow powder. Yield: 210
mg (72%). Crystals suitable for X-ray were obtained from a
concentrated hexanes solution at -35 °C. 1H NMR (500 MHz,
4.30 (s, 2H, Cp), 0.67 (vt, N = 10 Hz, 6H, CH3), 0.58 (vt, N = 10
Hz, 6H, CH3), -11.58 (dt, 2JH-P = 31.6 Hz, 1JH-Rh = 21.6 Hz, 1H, Rh-
1
= 162.0 (q, JB-C = 51.2 Hz,
H). 13C{1H} NMR (125 MHz, C6D6):
δ
ipso-C6H3(CF3)2), 135.8 (vt, N = 50.6 Hz, ArC), 135.2 (s, o-
C6H3(CF3)2), 130.7 (s, ArC), 130.0 (br, ArC), 129.9 (q, 2JC-F = 31.4
Hz, m-C6H3(CF3)2), 128.6 (s, ArC), 125.8 (q, 1JC-F = 272.4 Hz, CF3),
118.6 (s, p-C6H3(CF3)2), 92.8 (s, Cp), 89.2 (s, Cp), 21.6 (vt, N =
C6D6):
1.90 (m, 48H, Cy). 13C{1H} NMR (125 MHz, C6D6):
δ = 2.40-2.62 (br, 6H, Cy), 2.10-2.30 (br, 12H, Cy), 1.14-
δ = 200.9 (s,
COax), 198.8 (s, COeq), 35.6 (br, C1, Cy), 31.9 (s, C3,5, Cy), 30.7 (s,
33.0 Hz, CH3), 20.5 (vt, N = 37.0 Hz, CH3). 31P{1H} NMR (161
C3,5, Cy), 27.9 (br s, C2,6, Cy), 27.5 (br s, C2,6, Cy), 26.7 (s, C4, Cy).
1
MHz, C6D6):
MHz, C6D6):
δ
δ
= 13.6 (d, JP-Rh = 133.3 Hz). 11B{1H} NMR (128
31P{1H} NMR (201 MHz, C6D6):
δ
= 16.9 (s, satellites: JP-Pt
1
=
=
1
= -10.1 (s, -BArF ). 19F{1H} NMR (376 MHz, C6D6):
= -62.0 (s, CF3). Anal. Calcd. for C45H36BF18P2Rh: C, 49.39; H,
3
2412 Hz). 195Pt{1H} NMR (85.5 MHz, C6D6):
δ = -3645 (t, JP-pt
δ
3.32. C, 49.31; H, 3.62. Mp (°C): 152-155.
2447 Hz). IR (Nujol, cm−1): 1932 (br, υCO), 1984 (s, υCO), 2065 (s,
υCO). Anal. Calcd. for: C41H66Cl2GeO5P2PtW: C, 40.25; H, 5.44.
Found: C, 41.05; H, 5.51. Mp (°C): 120-123 (decomposes).
Reaction of [(CO)5W•GeCl2(η5-C5H4)]RhH(PMe2Ph)2
(1) with
K[HBsBu3]. To a 5 mL toluene solution of
1 (110 mg, 0.12
) with K[HBsBu3]. To a 5
(20 mg, 0.016 mmol), was added
mmol) was added K[HBsBu3] (254 μL, 1.0 M solution in THF,
0.25 mmol), and the mixture was stirred overnight. The
mother liquor was separated from the black precipitate by
filtration and the solvent was removed from the filtrate to
yield an orange oil containing a mixture of CpRh(PMe2Ph)2 and
sBu3B (as determined by 1H, 11B and 31P{1H} NMR spectroscopy
in C6D6).33
Reaction of ClPt(PCy3)2GeCl•W(CO)5 (
mL THF solution of
5
5
K[HBsBu3] (34 μL, 1.0 M solution in THF, 0.034 mmol), and the
mixture was stirred overnight. The solvent was removed from
the mixture to yield an dark orange oil containing a mixture of
PCy3 and sBu3B as soluble products.33
) with K[HBsBu3].
2 (96 mg, 0.10 mmol), was added
Synthesis of ClPt(PCy3)2SnCl•W(CO)5 (6). A 3 mL toluene
Reaction of CpRh(PMe2Ph)2•SnCl2•W(CO)5 (
2
solution of Pt(PCy3)2 (180 mg, 0.24 mmol) was added dropwise
to a 3 mL toluene solution of (THF)2SnCl2•W(CO)5 (130 mg,
0.24 mmol). The reaction mixture was stirred for 24 hrs and
the volatiles were removed under vacuum. 5 mL of hexanes
was then added to the oily product followed by stirring for one
To a 5 mL toluene solution of
K[HBsBu3] (210 μL, 1.0 M solution in THF, 0.21 mmol), and the
mixture was stirred overnight. The mother liquor was
separated from the black precipitate by filtration and the
6 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C5DT03018H
ARTICLE
Bohnen, J. Kreutzberg, D. Bl
Chem. Commun., 1993, 1136.
ӓ
ser and R. Boese, J. Chem. Soc.,
hour. The precipitate was separated from the mother liquor
and dried under vacuum to give a red powder. A few crystals
suitable for X-ray crystallography were grown from the
mixture in hexanes at -35 °C. The crystallographic data
identified one of the products as ClPt(PCy3)2SnCl•W(CO)5,
whereas the 31P{1H} and 195Pt{1H} NMR spectroscopy on the
product indicated the presence of two products with the
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Acknowledgements
This work was supported by the Natural Science and
Engineering Research Council of Canada (Discovery Grant for
E.R.) and the Canada Foundation for Innovation (CFI). The
authors also acknowledge Dr. Tapas Purkait for experimental
assistance. The authors also thank Dr. Christian Hering-
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(b) A. K. Swarnakar, S. M. McDonald, K. C. Deutsch, P. Choi,
M. J. Ferguson, R. McDonald and E. Rivard, Inorg. Chem.,
2014, 53, 8662. For important early work, see: (c) N. Kuhn, H.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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ARTICLE
Journal Name
24. H. Braunschweig, K. Gruss and K. Radacki, Inorg. Chem.,
2008, 47, 8595.
25. H. Braunschweig, P. Brenner, P. Cogswell, K. Kraft and K.
Schwab, Chem. Commun., 2010, 46, 7894.
26. A. B. Pangborn, M. A. Giardello, R. H. Grubbs, R. K. Rosen and
F. J. Timmers, Organometallics, 1996, 15, 1518.
27. A. L. Balch and D. E. Oram, Organometallics, 1988, 7, 155.
28. E. L. Kolychev, T. Bannenberg, M. Freytag, C. G. Daniliuc, P.
G. Jones and M. Tamm, Chem. Eur. J., 2012, 18, 16938.
29. H. Hope, Prog. Inorg. Chem., 1994, 41, 1.
30. R. H. Blessing, Acta Crystallogr., 1995, A51, 33.
31. G. M. Sheldrick, Acta Crystallogr., 2008, A64, 112.
32. P. T. Beurskens, G. Beurskens, R. de Gelder, J. M. M. Smits, S.
Garcia-Garcia and R. O. Gould, DIRDIF-2008; Crystallography
Laboratory, Radboud University: Nijmegen, The Netherlands,
2008.
33. M. Zaidlewicz and M. Krzeminski, Sci. Synth., 2004, 6, 1097.
TOC Graphic
The main group element triggered C-H bond activation of a
Rh-bound Cp ligand is reported. The key aspect of this
transformation is the presence of a highly Lewis acidic Group
14 element site.
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Supporting Information
Transition Metal-mediated Donor-acceptor Coordination of Low-oxidation
State Group 14 Element Halides
Anindya K. Swarnakar, Michael J. Ferguson, Robert McDonald, and Eric Rivard*
Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, Edmonton,
Alberta, Canada T6G 2G2.
Contents
Crystallographic data of compound 1-6
S2
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Table S1. Crystallographic data for compound 1
A. Crystal Data
formula
C H Cl GeO P RhW
26 27
2
5 2
formula weight
crystal dimensions (mm)
crystal system
space group
911.66
0.27×0.14×0.11
monoclinic
P2 /n (an alternate setting of P2 /c [No. 14])
1
1
a
unit cell parameters
a (Å)
b (Å)
c (Å)
8.9888 (3)
24.3719 (7)
14.4140 (4)
104.3064 (3)
3059.81 (16)
4
β (deg)
3
V (Å )
Z
-3
ρ
(g cm )
µ (mm )
1.979
5.572
calcd
-1
B. Data Collection and Refinement Conditions
b
diffractometer
Bruker D8/APEX II CCD
radiation (λ [Å])
graphite-monochromated Mo Kα (0.71073)
temperature (°C)
–100
scan type
data collection 2θ limit (deg)
total data collected
ω scans (0.3°) (15 s exposures)
56.65
28051 (-11≤h≤11, -32≤k≤31, -19≤l≤19)
independent reflections
number of observed reflections (NO)
structure solution method
refinement method
7477 (R = 0.0162)
int
2
2
7036 [F ≥ 2σ(F )]
o
o
c
Patterson/structure expansion (DIRDIF–2008 )
full-matrix least-squares on F (SHELXL–2013 )
2
d
absorption correction method
range of transmission factors
data/restraints/parameters
Gaussian integration (face-indexed)
0.6400–0.3265
7477 / 0 / 351
e
goodness-of-fit (S) [all data]
1.058
f
final R indices
2
2
R [F ≥ 2σ(F )]
0.0160
0.0379
1.032 and –0.480 e Å
1
o
o
wR [all data]
2
-3
largest difference peak and hole
a
Obtained from least-squares refinement of 9932 reflections with 4.44° < 2θ<56.48°.
b
Programs for diffractometer operation, data collection, data reduction and absorption correction
were those supplied by Bruker.
c
P. T. Beurskens, G. Beurskens, R. de Gelder, J. M. M. Smits, S. Garcia-Granda and R. Gould,
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O. (2008). The DIRDIF-2008 program system. Crystallography Laboratory, Radboud
University Nijmegen,
d
e
G. M. Sheldrick, Acta Crystallogr.2008, A64, 112–122.
2
2 2
1/2
S = [Σw(F – F ) /(n – p)] (n = number of data; p = number of parameters varied; w =
o
c
2
2
2
-1
2
2
[σ (F ) + (0.0187P) + 1.4453P] where P = [Max(F , 0) + 2F ]/3).
o
o
c
f
2
2 2
4 1/2
R = Σ||F | – |F ||/Σ|F |; wR = [Σw(F – F ) /Σw(F )]
.
1
o
c
o
2
o
c
o
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Table S2. Crystallographic data for compound 2
A. Crystal Data
formula
C
H
Cl O P RhSnW
26.25 27.5 2.5 5 2
formula weight
crystal dimensions (mm)
crystal system
space group
979.00
0.27 × 0.02 × 0.02
monoclinic
P2 /n (an alternate setting of P2 /c [No. 14])
1
1
a
unit cell parameters
a (Å)
b (Å)
c (Å)
15.3972 (2)
9.0453 (1)
23.3877 (3)
90.5374 (12)
3257.12 (7)
4
β (deg)
3
V (Å )
Z
-3
ρ
(g cm )
µ (mm )
1.996
19.58
calcd
-1
B. Data Collection and Refinement Conditions
b
diffractometer
Bruker D8/APEX II CCD
radiation (λ [Å])
temperature (°C)
Cu Kα (1.54178) (microfocus source)
–100
scan type
data collection 2θ limit (deg)
total data collected
ω and φ scans (1.0°) (5 s exposures)
145.17
21691 (-19≤h≤18, -11≤k≤11, -28≤l≤28)
independent reflections
number of observed reflections (NO)
structure solution method
refinement method
6344 (R = 0.0781)
int
2
2
5092 [F ≥ 2σ(F )]
o
o
c
Patterson/structure expansion (DIRDIF–2008 )
full-matrix least-squares on F (SHELXL–2013 )
2
d,e
absorption correction method
range of transmission factors
data/restraints/parameters
Gaussian integration (face-indexed)
0.8514–0.1190
6344 / 0 / 347
f
goodness-of-fit (S) [all data]
1.031
g
final R indices
2
2
R [F ≥ 2σ(F )]
0.0345
0.0868
1.130 and –1.373 e Å
1
o
o
wR [all data]
2
-3
largest difference peak and hole
a
Obtained from least-squares refinement of 9963 reflections with 6.84° < 2θ<143.88°.
b
Programs for diffractometer operation, data collection, data reduction and absorption correction
were those supplied by Bruker.
c
P. T. Beurskens, G. Beurskens, R. de Gelder, J. M. M. Smits, S. Garcia-Granda and R. Gould,
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O. (2008). The DIRDIF-2008 program system. Crystallography Laboratory, Radboud
University Nijmegen,
d
e
G. M. Sheldrick, Acta Crystallogr.2008, A64, 112–122.
Attempts to refine peaks of residual electron density as disordered or partial-occupancy solvent
dichloromethane chlorine or carbon atoms were unsuccessful. The data were corrected for
disordered electron density through use of the SQUEEZE procedure (P. van der Sluis and A.
L. Spek, Acta Crystallogr.1990, A46, 194–201) as implemented in PLATON (A.L. Spek,
Acta Crystallogr.1990, A46, C34; A. L. Spek, J. Appl. Cryst.2003, 36, 7–13. PLATON - a
multipurpose crystallographic tool. UtrechtUniversity, Utrecht, The Netherlands). A total
3
solvent-accessible void volume of 225.6Å with a total electron count of 43 (consistent with
one molecule of solvent CH Cl , or 0.25 molecule per formula unit of the metal complex
2
2
molecule) was found in the unit cell.
f
2
2 2
1/2
S = [Σw(F – F ) /(n – p)] (n = number of data; p = number of parameters varied; w =
o
2
c
2
2
-1
2
2
[σ (F ) + (0.0403P) + 0.9612P] where P = [Max(F , 0) + 2F ]/3).
o
o
c
g
2
2 2
4 1/2
R = Σ||F | – |F ||/Σ|F |; wR = [Σw(F – F ) /Σw(F )]
.
1
o
c
o
2
o
c
o
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Table S3. Crystallographic data for compound 3
A. Crystal Data
formula
C H Cl P PbRh
21 27 2 2
formula weight
crystal dimensions (mm)
crystal system
space group
722.36
0.09 × 0.08 × 0.07
monoclinic
P2 /n (an alternate setting of P2 /c [No. 14])
1
1
a
unit cell parameters
a (Å)
b (Å)
c (Å)
17.346 (5)
15.351 (4)
18.164 (5)
95.470 (3)
4814 (2)
8
β (deg)
3
V (Å )
Z
-3
ρ
(g cm )
µ (mm )
1.993
8.030
calcd
-1
B. Data Collection and Refinement Conditions
b
diffractometer
Bruker D8/APEX II CCD
radiation (λ [Å])
graphite-monochromated Mo Kα (0.71073)
temperature (°C)
–100
scan type
data collection 2θ limit (deg)
total data collected
ω scans (0.3°) (20 s exposures)
55.52
41795 (-22 ≤h≤ 22, -19 ≤k≤ 19, -23 ≤l≤ 23)
independent reflections
number of observed reflections (NO)
structure solution method
refinement method
11064 (R = 0.0573)
int
2
2
8280 [F ≥ 2σ(F )]
o
o
c
intrinsic phasing (SHELXT-2014 )
full-matrix least-squares on F (SHELXL–2013 )
2
c
absorption correction method
range of transmission factors
data/restraints/parameters
Gaussian integration (face-indexed)
0.7619–0.5292
11064 / 0 / 495
d
goodness-of-fit (S) [all data]
1.120
e
finalR indices
2
2
R [F ≥ 2σ(F )]
0.0364
0.0816
1.992 and –1.824 e Å
1
o
o
wR [all data]
2
-3
largest difference peak and hole
a
Obtained from least-squares refinement of 9990 reflections with 4.50° < 2θ<53.30°.
b
Programs for diffractometer operation, data collection, data reduction and absorption correction
were those supplied by Bruker.
d
d
G. M. Sheldrick, Acta Crystallogr.2008, A64, 112–122.
2
2 2
1/2
S = [Σw(F – F ) /(n – p)] (n = number of data; p = number of parameters varied; w =
o
c
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2
2
2 -1
2
2
[σ (F ) + (0.0316P) ] where P = [Max(F , 0) + 2F ]/3).
o
o
c
e
2
2 2
4 1/2
R = Σ||F | – |F ||/Σ|F |; wR = [Σw(F – F ) /Σw(F )]
.
1
o
c
o
2
o
c
o
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Table S4. Crystallographic data for compound 4
A. Crystal Data
formula
C H BF P Rh
48 43 18 2
formula weight
crystal dimensions (mm)
crystal system
space group
1137.48
0.26×0.20×0.16
triclinic
P (No. 2)
a
unit cell parameters
a (Å)
b (Å)
c (Å)
12.2135 (3)
12.5991 (3)
17.0103 (4)
80.6961 (10)
81.3382 (8)
75.2500 (8)
2481.49 (10)
2
α (deg)
β (deg)
γ (deg)
3
V (Å )
Z
-3
ρ
(g cm )
µ (mm )
1.522
4.305
calcd
-1
B. Data Collection and Refinement Conditions
b
diffractometer
Bruker D8/APEX II CCD
radiation (λ [Å])
temperature (°C)
Cu Kα (1.54178) (microfocus source)
–100
scan type
data collection 2θ limit (deg)
total data collected
ω and φ scans (1.0°) (5 s exposures)
144.46
17405 (-15≤h≤15, -15≤k≤15, -21≤l≤20)
independent reflections
number of observed reflections (NO)
structure solution method
refinement method
9416 (R = 0.0129)
int
2
2
9241 [F ≥ 2σ(F )]
o
o
c
intrinsic phasing (SHELXT-2014 )
full-matrix least-squares on F (SHELXL–2014 )
2
d.e
absorption correction method
range of transmission factors
data/restraints/parameters
Gaussian integration (face-indexed)
0.6786–0.4912
9416 / 0 / 716
f
goodness-of-fit (S) [all data]
1.026
g
final R indices
2
2
R [F ≥ 2σ(F )]
0.0319
0.0860
1.112 and –0.806 e Å
1
o
o
wR [all data]
2
-3
largest difference peak and hole
a
Obtained from least-squares refinement of 9844 reflections with 8.46° < 2θ<144.24°.
Programs for diffractometer operation, data collection, data reduction and absorption correction
b
were those supplied by Bruker.
c
G. M. Sheldrick, Acta Crystallogr.2015, A71, 3–8. (SHELXT-2014)
S8

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d
e
G. M. Sheldrick, G. M. Acta Crystallogr.2015, C71, 3–8. (SHELXL-2014)
Attempts to refine peaks of residual electron density as disordered or partial-occupancy solvent
hexane carbon atoms were unsuccessful. The data were corrected for disordered electron
density through use of the SQUEEZE procedureas implemented in PLATON (A. L. Spek,.
Acta Crystallogr.2015, C71, 9–18. PLATON - a multipurpose crystallographic tool.
UtrechtUniversity, Utrecht, The Netherlands). A total solvent-accessible void volume of
3
221Å with a total electron count of 50 (consistent with 1 molecule of solvent hexane, or 0.5
molecules per formula unit of the rhodium complex) was found in the unit cell.
f
2
2 2
1/2
S = [Σw(F – F ) /(n – p)] (n = number of data; p = number of parameters varied; w =
o
2
c
2
2
-1
2
2
[σ (F ) + (0.0493P) + 2.1386P] where P = [Max(F , 0) + 2F ]/3).
o
o
c
g
2
2 2
4 1/2
R = Σ||F | – |F ||/Σ|F |; wR = [Σw(F – F ) /Σw(F )]
.
1
o
c
o
2
o
c
o
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Table S5. Crystallographic data for compound 5
A. Crystal Data
formula
C H Cl GeO P PtW
44 73
2
5 2
formula weight
crystal dimensions (mm)
crystal system
space group
1266.39
0.29×0.09×0.06
triclinic
P (No. 2)
1
a
unit cell parameters
a (Å)
b (Å)
c (Å)
10.172 (2)
12.807 (3)
20.478 (4)
105.848 (2)
103.959 (2)
93.004 (3)
2470.6 (8)
2
α (deg)
β (deg)
γ (deg)
3
V (Å )
Z
-3
ρ
(g cm )
µ (mm )
1.702
5.964
calcd
-1
B. Data Collection and Refinement Conditions
b
diffractometer
BrukerD8/APEX II CCD
radiation (λ [Å])
graphite-monochromated Mo Kα (0.71073)
temperature (°C)
–100
scan type
data collection 2θ limit (deg)
total data collected
ω scans (0.3°) (20 s exposures)
55.18
22384 (-13≤h≤13, -16≤k≤16, -26≤l≤26)
independent reflections
number of observed reflections (NO)
structure solution method
refinement method
11338 (R = 0.0148)
int
2
2
9930 [F ≥ 2σ(F )]
o
o
c
intrinsic phasing (SHELXT )
2
c
full-matrix least-squares on F (SHELXL–2013 )
Gaussian integration (face-indexed)
0.7960–0.3812
absorption correction method
range of transmission factors
data/restraints/parameters
d
11338 / 3 / 534
e
goodness-of-fit (S) [all data]
1.117
f
final R indices
2
2
R [F ≥ 2σ(F )]
0.0212
0.0603
1.248 and –1.042 e Å
1
o
o
wR [all data]
2
-3
largest difference peak and hole
a
Obtained from least-squares refinement of 9783 reflections with 4.46° < 2θ<55.04°.
b
Programs for diffractometer operation, data collection, data reduction and absorption correction
were those supplied by Bruker.
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c
G. M. Sheldrick, ActaCrystallogr.2008, A64, 112–122.
d
The C–C distances within the minor component of the disordered solvent hexane molecule were
restrained to be approximately equal by use of the SHELXLSADI instruction.
e
2
2 2
1/2
S = [Σw(F – F ) /(n – p)] (n = number of data; p = number of parameters varied; w =
o
c
2
2
2
-1
2
2
[σ (F ) + (0.0333P) + 0.5140P] where P = [Max(F , 0) + 2F ]/3).
o
o
c
f
2
2 2
4 1/2
R = Σ||F | – |F ||/Σ|F |; wR = [Σw(F – F ) /Σw(F )]
.
1
o
c
o
2
o
c
o
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Table S6. Crystallographic data for compound 6
A. Crystal Data
formula
C H Cl O P PtSnW
41 66
2 5 2
formula weight
crystal dimensions (mm)
crystal system
space group
1355.58
0.23×0.18×0.09
orthorhombic
P2 2 2 (No. 19)
1 1 1
a
unit cell parameters
a (Å)
b (Å)
c (Å)
V (Å )
Z
14.8910 (4)
16.3240 (4)
22.1599 (6)
5386.6 (2)
4
3
-3
ρ
(g cm )
µ (mm )
1.672
5.379
calcd
-1
B. Data Collection and Refinement Conditions
b
diffractometer
Bruker D8/APEX II CCD
radiation (λ [Å])
graphite-monochromated Mo Kα (0.71073)
temperature (°C)
–100
scan type
data collection 2θ limit (deg)
total data collected
ω scans (0.3°) (20 s exposures)
54.98
47820 (-19≤h≤19, -21≤k≤21, -28≤l≤28)
independent reflections
number of observed reflections (NO)
structure solution method
refinement method
12339 (R = 0.0289)
int
2
2
11780 [F ≥ 2σ(F )]
o
o
c
intrinsic phasing (SHELXT )
2
c
full-matrix least-squares on F (SHELXL–2013 )
Gaussian integration (face-indexed)
0.6982–0.4584
absorption correction method
range of transmission factors
data/restraints/parameters
d
12339 / 18 / 512
e
Flack absolute structure parameter
0.0093(19)
1.005
f
goodness-of-fit (S) [all data]
g
final R indices
2
2
R [F ≥ 2σ(F )]
0.0176
0.0404
0.737 and –0.323 e Å
1
o
o
wR [all data]
2
-3
largest difference peak and hole
a
Obtained from least-squares refinement of 9906 reflections with 4.44° < 2θ<51.62°.
b
Programs for diffractometer operation, data collection, data reduction and absorption correction
were those supplied by Bruker.
c
G. M. Sheldrick, Acta Crystallogr.2008, A64, 112–122.
d
Distances within the disordered solvent n-hexane molecule were restrained to idealized target
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distances during refinement: d(C1SA–C2SA) = d(C2SA–C3SA) = d(C3SA–C4SA) =
d(C4SA–C5SA) = d(C5SA–C6SA) = d(C1SB–C2SB) = d(C2SB–C3SB) = d(C3SB–C4SB)
…
…
…
= d(C4SA–C5SB) = d(C5SB–C6SB) = 1.50(1) Å; d(C1SA C3SA) = d(C2SA C4SA) =
…
…
…
d(C3SA C5SA) = d(C4SA C6SA) = d(C1SB C3SB) = d(C2SB C4SB) =
…
…
d(C3SB C5SB) = d(C4SB C6SB) = 2.45(1) Å.
e
f
H. D. Flack, Acta Crystallogr.1983, A39, 876–881; H. D. Flack, G. Bernardinelli, Acta
Crystallogr.1999, A55, 908–915; H.D. Flack, G. Bernardinelli, J. Appl. Cryst.2000, 33,
1143–1148. The Flack parameter will refine to a value near zero if the structure is in the
correct configuration and will refine to a value near one for the inverted configuration.
2
2 2
1/2
S = [Σw(F – F ) /(n – p)] (n = number of data; p = number of parameters varied; w =
o
c
2
2
2 -1
2
2
[σ (F ) + (0.0115P) ] where P = [Max(F , 0) + 2F ]/3).
o
o
c
g
2
2 2
4 1/2
R = Σ||F | – |F ||/Σ|F |; wR = [Σw(F – F ) /Σw(F )]
.
1
o
c
o
2
o
c
o
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181x47mm (300 x 300 DPI)